DE69027978T2 - Color photographic silver halide material - Google Patents

Description

FIELD OF INVENTION:

The present invention relates to a silver halide color photographic material capable of being rapidly processed and in which variations in cyan dye density caused by changes in the composition of processing solutions are prevented. The photographic material can provide images whose deterioration during storage in the form of prints caused by variations in cyan dye density subsequent to color development processing is suppressed.

BACKGROUND OF THE INVENTION:

In the formation of color photographic images, light-sensitive layers containing color photographic yellow, magenta and cyan couplers are exposed imagewise and then processed with a color developer solution containing a color developing agent. In this process, the couplers undergo a coupling reaction with a Oxidation product of an aromatic primary amine, thereby providing colored dyes.

Standard processing steps for silver halide color photographic materials generally include a color development step during which a color image is formed, a silver removal step in which developed silver and undeveloped silver are removed, and water washing and/or image stabilization steps.

Attempts have been made to reduce processing time and there has been an increased need to reduce this processing time recently due to the need to deliver finished prints in a shorter time, and attempts to reduce the work in laboratories and to reduce the size and simplify the procedures for small laboratory processing systems, also called "mini-laboratories".

The reduction in time associated with the color development step can be achieved by appropriately combining the following techniques: using a coupler having as high a coupling rate as possible, using a silver halide emulsion with a high processing speed, using a color developing solution with a high developing speed and raising the temperature of the color developing solution.

The reduction of the time for the desilvering or silver removal step can be achieved by Lowering the pH of either a bleaching solution or a bleach-fixing solution. Such acceleration of bleaching and fixing by lowering the pH of the bleach-fixing solution is described in "The Theory of the Photographic Process", edited by T.H. James, Chapter 15, E. Bleach-Fix System.

However, accelerating the bleaching step by lowering the pH of the bleach-fixing solution may cause deterioration of image quality because the dyes formed from cyan couplers are converted to their leuco form, thereby becoming decolored, and do not return to their colored form before processing is completed (hereinafter, this phenomenon is referred to as "color restoration failure"), thereby causing an undesirable decrease in density. After processing, color restoration gradually destroys the color balance of the image.

To solve this problem, the color-developed photosensitive materials are washed with water, thereby removing the color developing agent before the bleach-fixing step. However, this technique requires the number of processing steps to be increased, thereby lengthening the overall processing time.

Alternatively, a water-soluble ionic compound containing a polyvalent element may be added to the bleach-fix bath, as proposed in US-PS 3,773,510. However, this technique increases environmental pollution without fully achieving the objectives discussed above.

On the other hand, the conventional use of hydroquinones or quinones for controlling gradation, preventing fogging and preventing fading of magenta dyes, as well as for other purposes, is described, for example, in JP-A-55-161238, JP-A-60-60647, JP-A-53-32034 (the term "JP-A-" as used herein means an "unexamined published Japanese patent application"), DE-A1 2 149 789 and 3 320 483, JP-A-58-24141, JP-A-46-2128, JP-B-43-4934, JP-B-50-21249, JP-B-60-3171 (the term "JP-B-" as used herein means an "examined Japanese patent application"). Patent Publication"), JP-A-49-106329, JP-A-49-129535, GB-PS 1 465 081, JP-A-49-129536, JP-A-49-134327, JP-A-50-110337, JP-A-50-156438, JP-A-51-6024, JP-A-51-9828, JP-A-51-14023, JP-A-52-65432, JP-A-52-128130, JP-A-52-146234, JP-A-52-146235, TP-A-53-9528, JP-A-53-55121, JP-A-53-139533, JP-A-54-24019, JP-A-54-25823, JP-A-54-29637, JP-A-54-70036, JP-A-54-97021, JP-A-54-133181, JP-A-55-95948, JP-A-56-5543, JP-A-56-83742, JP-A-56-85748, JP-A-56-87040, JP-A-56-153342, JP-A-57-112749, JP-A-57-176038, JP-A-58-136030, JP-A-59-72443, JP-A-59-75249, JP-A-59-83162, JP-A-59-101650, JP-A-59-180557, JP-A-60-60647, JP-A-59-189342, JP-A-59-191031, JP-A-60-55339 and JP-A-60-263149, Research Disclosure, Vol. 228, No. 2287 (1983) and U.S. Patent Nos. 2,384,658, 2,403,721, 2,728,659, 2,735,765, 3,700,453, 2,675,314, 2,732,300 and 2,360 290. In particular, the prevention of obfuscation by using hydroquinones containing an electron-attracting group substituted, in an intermediate layer is described, for example, in JP-B-59-35012, JP-A-56-109344 and JP-A-57-22237. However, in the above-mentioned publications, the problem of color restoration failure is not discussed.

Since hydroquinones can cause color recovery failure when used in combination with a bleach-fixing solution having a relatively high pH and contaminated with a color developing solution, the use of reduced amounts of hydroquinones has been proposed, e.g. in JP-A-60-60647.

Furthermore, JP-A-63-316857 relates to a method for preventing color restoration failure, wherein a bleach-fixing solution having a low pH value containing hydroquinones or quinones each substituted with an alkyl group is used. Although this method had an effect of preventing color restoration failure, further improvements are still required in this area. In addition, cyan color images provided by this method may be deteriorated if the developed photographic materials are kept under light of very high illuminances.

SUMMARY OF THE INVENTION:

An object of the invention is to provide a silver halide color photographic material which is can be processed quickly in such a way that a sufficiently high colour density can be achieved within a short period of time.

Another object of the present invention is to provide a silver halide color photographic material wherein the color restoration failure of the cyan dye image is improved while preventing the deterioration of image quality due to destruction of the image color balance after processing.

Another object of the invention is to provide a silver halide color photographic material which provides cyan color images with good preservability.

Further objects according to the invention will become clear from the following description and claims.

According to the foregoing objects, the present invention relates to a multilayer silver halide color photographic material comprising a support having thereon a yellow color-forming silver halide emulsion layer, a magenta color-forming silver halide emulsion layer and a cyan color-forming silver halide emulsion layer, wherein the cyan color-forming silver halide emulsion layer contains at least one oil-soluble cyan coupler capable of reacting with an oxidation product of an aromatic primary amine developing agent to form a substantially diffusion-resistant dye and which is represented by the formula (I) described below, at least one element selected from the compounds represented by the formulas (II) and (III) described below, and at least one compound of the formula (IV) described below

wherein

Y represents -NHCO- or -CONH;

R₁ represents an alkyl group, an aryl group, a heterocyclic group or an amino group;

X represents a hydrogen atom, a halogen atom, an alkoxy group or an acylamino group;

R₂ represents an alkyl group or an acylamino group or, when bonded to X, a non-metal atom forming a 5- to 7-membered ring;

Z represents a hydrogen atom or a group capable of being released by coupling with an oxidation product of a developing agent;

R₃ and R₅ each represent a halogen atom;

R₄ and R₆ each represent an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amido group, an acyl group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group or a sulfoxide group, with the proviso that each of these groups has 6 or more carbon atoms; and

R₇, R₈, R₇ and R₁₀ each represent a hydrogen atom, an aliphatic group, a aromatic group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group or a carbamoyl group, or R₇ and R₈ or R₄ and R₁₀ may be combined with each other to form a 5- to 7-membered ring, with the provisos that R₇, R₈, R₁₀ and R₁₀ do not simultaneously represent hydrogen atoms and the total number of carbon atoms included therein is 8 to 60.

DETAILED DESCRIPTION OF THE INVENTION:

In the photographic material of the present invention, the color restoration failure and light fading are further improved by incorporating at least one high boiling organic solvent having a viscosity of not less than 200 cp (at 25°C) into the cyan color forming layer of the color photographic material.

Furthermore, the color restoration failure and light fading are further improved by incorporating a water-insoluble organic polymer compound into the cyan color-forming layer of the color photographic material.

The oil-soluble cyan coupler of formula (I) and the compound of formula (II) or (III) used in the present invention are described in detail below.

In formula (I), R&sub1; an alkyl group, preferably a straight-chain, branched or cyclic alkyl group having 1 to 32 carbon atoms (e.g. methyl, butyl, pentadecyl or cyclohexyl), an aryl group (e.g. phenyl or naphthyl), a heterocyclic group (e.g. 2-pyridyl, 3-pyridyl, 2-furanyl or 2-oxazolyl) or an amino group, which are preferably substituted with one or more substituents selected from an alkyl group, an aryl group, an alkyl or aryloxy group (e.g. methoxy, dodecyloxy, methoxyethoxy, phenyloxy, 2,4-di-tert-amylphenoxy, a 3-tert-butyl-4-hydroxyphenyloxy group or naphthyloxy), a carboxy group, an alkyl or arylcarbonyl group (e.g. acetyl, tetradecanoyl or benzoyl), an alkyl or aryloxycarbonyl group (e.g. methoxycarbonyl, benzyloxycarbonyl or phenoxycarbonyl), an acyloxy group (e.g. acetyloxy, benzoyloxy or phenylcarbonyloxy), a sulfamoyl group (e.g. N-ethylsulfamoyl or N-octadecylsulfamoyl), a carbamoyl group (e.g. N-ethylcarbamoyl or N-methyldodecylcarbamoyl), a sulfonamido group (e.g. methanesulfonamido or benzenesulfonamido), an acylamino group (e.g. acetylamino, benzamido, ethoxycarbonylamino or phenylaminocarbonylamino), an imido group (e.g. succinimido or hydantoinyl), a sulfonyl group (e.g. methanesulfonyl), a hydroxy group, a cyano group, a nitro group and a halogen atom.

In formula (I), R₂ preferably represents an alkyl group having 1 to 20 carbon atoms (e.g. methyl, ethyl, butyl or pentadecyl) or an acylamino group (e.g. tetradecanoylamino, benzoylamino or 2-(2,4-ditert-amylphenoxy)butanamido). The alkyl group represented by R₂ may be substituted with one or more substituents selected from those described for R₁.

In formula (I), X represents a hydrogen atom, a halogen atom (e.g. fluorine, chlorine or bromine), an alkoxy group (e.g. methoxy or butoxy) or an acylamino group (e.g. acetamido).

Condensed ring type cyan couplers in which R2 and X are bonded together to form a 5-, 6- or 7-membered ring are also preferred as the compound of formula (I), as are the phenolic cyan couplers described above. Particularly preferred examples of such condensed ring type couplers are oxyindole type and imidazol-2-one type cyan couplers.

In formula (I), Z represents a hydrogen atom or a coupling group such as a halogen atom (e.g. fluorine, chlorine or bromine), an alkoxy group (e.g. ethoxy, dodecyloxy, methoxycarbamoylmethoxy, carboxypropyloxy or methylsulfonylethoxy), an aryloxy group (e.g. 4-chlorophenoxy, 4-methoxyphenoxy or 4-carboxyphenoxy), an acyloxy group (e.g. acetoxy, tetradecanoyloxy or benzoyloxy), a sulfonyloxy group (e.g. methanesulfonyloxy or toluenesulfonyloxy), an amido group (e.g. dichloroacetylamino, heptabutyrylamino, methanesulfonylamino or toluenesulfonylamino), an alkoxycarbonyloxy group (e.g. ethoxycarbonyloxy or benzyloxycarbonyloxy), an aryloxycarbonyloxy group (e.g. phenoxycarbonyloxy), an aliphatic or aromatic thio group (e.g. ethylthio, Phenylthio or Tetrazolylthio), an imido group (eg succinimido or hydantoinyl), an N-containing heterocyclic group (eg 1-pyrazolyl or 1-benzotriazolyl), an aromatic azo group (eg phenylazo). These coupling groups may contain a photographically useful group.

In formulas (II) and (III), R₃ and R₅ each represent a halogen atom, preferably chlorine or bromine.

In formulas (II) and (III), R₄ and R₆ represent in each case an alkyl group, preferably a straight-chain or branched alkyl group having 6 to 40 carbon atoms (e.g. sec-dodecyl, n-hexadecyl or sec-icosyl), an aryl group, preferably having 6 to 40 carbon atoms (e.g. phenyl or p-tolyl), an alkoxy group, preferably having 6 to 40 carbon atoms (e.g. tetradecyloxy or hexadecyloxy), an aryloxy group, preferably having 6 to 40 carbon atoms (e.g. phenoxy or p-acetamidophenoxy), an alkylthio group, preferably having 6 to 40 carbon atoms (e.g. dodecylthio or octadecylthio), an arylthio group, preferably having 6 to 40 carbon atoms (e.g. phenylthio), an amido group, preferably having 6 to 40 carbon atoms (e.g. benzoylamino or hexadecanamido), an acyl group, preferably having 6 to 40 carbon atoms (eg benzoyl or hexadecanoyl), a sulfonyl group, an aliphatic or aromatic sulfonyl group, preferably having 6 to 40 carbon atoms (eg benzenesulfonyl or 4-dodecyloxybenzenesulfonyl), an alkoxycarbonyl group, preferably having 6 to 40 carbon atoms (eg hexadecyloxycarbonyl), an aryloxycarbonyl group, preferably having 7 to 40 carbon atoms (eg Phenoxycarbonyl), a carbamoyl group, preferably having 6 to 40 carbon atoms (eg N-dodecylcarbamoyl or N,N-diphenylcarbamoyl), a sulfamoyl group, preferably having 6 to 40 carbon atoms (eg N,N-dihexylsulfamoyl or N-phenylsulfamoyl) or a sulfoxide group, preferably having 1 to 40 carbon atoms (eg hexadecane sulfoxide). The number of carbon atoms present in the substituent represented by R₄ or R₆ is 6 or more.

The compound of formula (II) or (III) may be a dimer, a trimer, an oligomer or a polymer.

In formula (I), Y preferably represents -NHCO-.

In formula (I), R₁ preferably represents an alkyl group or an aryl group, with an alkyl group being particularly preferred.

In formula (I), R₂ preferably represents an alkyl group containing 1 to 15 carbon atoms, with 1 to 4 carbon atoms being particularly preferred.

In formula (I), Z preferably represents a hydrogen atom or a halogen atom, with a halogen atom being particularly preferred.

In formula (I), X preferably represents a halogen atom. Those compounds wherein X and R₂ are bonded to each other to form a hetero ring are also preferred.

In formulas (II) and (III), R₄ and R₆ each preferably represent an alkyl group, an alkylthio group or an amido group, with an alkyl group being particularly preferred.

R₃ and R₄ in formula (II) and R₅ and R₆ in formula (III) are preferably each in 2,5-substitution with respect to one another.

Specific examples of the compounds of the formulas (I), (II) and (III) of the present invention are given below, but the present invention is not limited thereto.

Manufacturing processes for producing the cyan couplers of formula (I) are known, for example, from US Pat. Nos. 2,369,929, 4,518,687, 4,511,647 and 3,772,020 concerning phenolic cyan couplers having an alkyl group in the 5-position; from US Pat. Nos. 2,772,162, 2,895,826, 4,334,011 and 4,500,653 and JP-A-59-164555 concerning 2,5-diacylaminophenolic couplers; and from U.S. Patents 4,327,173, 4,564,586 and 4,430,423, JP-A-61-390441 and JP-A-62-257158 for such phenolic cyan couplers in which a nitrogen-containing hetero ring is condensed with the phenol nucleus.

The coating amount of the cyan coupler of the present invention is preferably 1.0 x 10⁻⁵ to 2.0 x 10⁻³ mol, more preferably 1.0 x 10⁻⁴ to 1.0 x 10⁻³ mol per m² of the photographic material.

The cyan coupler of the present invention can be used in a suitable mixture with one or more cyan couplers other than those of the present invention. In such a case, the cyan coupler of the present invention is preferably used in an amount of at least 5 mol%, more preferably at least 30 mol%, of the total amount of cyan coupler used.

The compounds of formulas (II) and (III) can be prepared according to the methods described, for example, in JP-A-56-109344 and JP-A-57-22237 and the following preparation examples.

MANUFACTURING EXAMPLE 1 Preparation of compound (III-3):

33.5 g (0.1 mol) of 2-sec-hexadecylhydroquinone was dissolved in 300 mL of methylene chloride, and to the resulting solution was added dropwise 8.1 mL (0.1 mol) of sulfuryl chloride with stirring at room temperature over a period of 30 minutes. After stirring at room temperature for 6 hours, the reaction mixture was left to stand overnight and extracted with ethyl acetate. The extract was washed with a 5% aqueous sodium chloride solution three times, dried over magnesium sulfate and concentrated. The residue was purified by column chromatography (solvent: chloroform) to obtain 27 g of the desired 2-chlorosec-hexadecylhydroquinone as a light from oily product. The structure was determined by NNR and mass spectrum.

Elemental analysis for C₂₂H₃�7ClO₂:

Calculated (%) : C 71.61 H 10.11

Found (%) : 71.38 10.35

MANUFACTURING EXAMPLE 2 Preparation of compound (II-2):

18.5 g (0.05 mol) of 2-chloro-5-sec-hexadecylhydroquinone from Preparation Example 1 were dissolved in 200 ml of ethyl acetate, the resulting solution was treated with 22 g powdered manganese dioxide was added and the mixture was stirred at 50°C for 8 hours. After cooling, the manganese dioxide was separated by filtration and the filtrate was concentrated. The residue was purified by column chromatography (solvent: chloroform) to obtain 15 g of the desired 2-chloro-5-sec-hexadecyl-1,4-benzoquinone as a yellow oily product. The structure was confirmed by NMR and mass spectrum.

Elemental analysis for C₂H₃₅ClO₂:

Calculated (%) C 72.01 H 9.11

Found (%) 71.87 9.35

The quinones represented by the formula (II) and the hydroquinones represented by the formula (III) of the present invention may be used independently or in combination. Furthermore, they may be used together with quinones and/or hydroquinones other than those of the present invention, particularly those described in JP-A-63-316857.

The quinone represented by the formula (II) and/or the hydroquinone represented by the formula (III) of the present invention can be used in an amount of 0.1 to 100 mol%, preferably 0.5 to 30 mol%, and most preferably 1 to 20 mol% per mol of the cyan coupler represented by the formula (I) of the present invention. In the case where the compound of the formula (II) is used together with the compound of the formula (III), the ratio of these two compounds to be used is freely selectable, with the preferred molar ratio of the compound of the formula (II) to the compound of formula (III) is 1:100 to 10:1.

The compound of formula (II) or (III) can be added to a coating solution for a photographic layer containing the cyan coupler of the present invention, either directly or by previously dissolving it in a solvent which does not adversely affect the photographic light-sensitive material, for example, in water or an alcohol. The compound can also be added by dissolving it in a high-boiling organic solvent and/or a low-boiling organic solvent and then emulsifying or dispersing the solution in an aqueous medium. In addition, the compound can be used by emulsifying or dispersing with the cyan coupler.

The hydroquinone and/or quinone according to the invention is preferably present in oil droplets containing the cyan coupler.

The use of the specific hydroquinone and/or quinone of the invention is particularly effective when a bleaching solution or a bleach-fixing solution is contaminated with a developing agent (i.e., a developing agent carried over from a pre-bath).

In the compound represented by formula (IV), R₇, R₈, R₃ and R₁₀ each represent a hydrogen atom, an aliphatic group, an aromatic group, an aliphatic oxycarbonyl group (eg dodecyloxycarbonyl or allyloxycarbonyl), an aromatic oxycarbonyl group (eg phenoxycarbonyl) or a carbamoyl group (eg tetradecylcarbamoyl, phenylmethylcarbamoyl), with the provisos that R₃, R₄, R�5 and R�6 do not simultaneously represent hydrogen atoms and the total number of carbon atoms within these groups is 8 to 60.

The term "aliphatic group" as used herein means an aliphatic hydrocarbon group which may be straight-chain, branched or cyclic and includes both saturated and unsaturated groups such as an alkyl group, an alkenyl group and an alkynyl group. Typical examples include a methyl group, an ethyl group, a butyl group, a dodecyl group, an octadecyl group, an icosenyl group, an isopropyl group, a tert-butyl group, a tert-octyl group, a tert-dodecyl group, a cyclohexyl group, a cyclopentyl group, an allyl group, a vinyl group, a 2-hexadecyl group and a propargyl group.

The aromatic group preferably represents a substituted or unsubstituted phenyl or naphthyl group containing 6 to 42 carbon atoms.

The aliphatic group and the aromatic group may be further substituted with a group or groups selected from an alkyl group, an aryl group, a heterocyclic group, an alkoxy group (eg methoxy or 2-methoxyethoxy), an aryloxy group (eg 2,4-ditert-amylphenoxy, 2-chlorophenoxy or 4-cyanophenoxy), an alkenyloxy group (eg 2-propenyloxy), a acyl group (e.g., acetyl or benzoyl), an ester group (e.g., butoxycarbonyl, phenoxycarbonyl, acetoxy, benzoyloxy, butoxysulfonyl or toluenesulfonyloxy), an amido group (e.g., acetylamino, ethylcarbamoyl, dimethylcarbamoyl, methanesulfonamido or butylsulfamoyl), a sulfamido group (e.g., dipropylsulfamoylamino), an imido group (e.g., succinimido or hydantoinyl), a ureido group (e.g., phenylureido or dimethylureido), an aliphatic or aromatic sulfonyl group (e.g., methanesulfonyl or phenylsulfonyl), an aliphatic or aromatic thio group (e.g., ethylthio or phenylthio), a hydroxyl group, a cyano group, a carboxyl group, a nitro group, a sulfo group and a halogen atom.

Specific examples of the compounds represented by formula (IV) which can be used in the present invention are shown below, but the present invention is not limited to these.

Regarding the preparation of the compound represented by formula (IV), for example, the compound (IV-9) can be prepared according to the process as described in Example 1 in column 11 of U.S. Patent No. 4,540,657, and other compounds can be prepared by referring to this process.

The compound of formula (IV) of the present invention is preferably present in oil droplets containing the cyan coupler of formula (I). The compound may be dissolved in any solvent, for example, ethyl acetate, together with the cyan coupler and, if desired, a water-insoluble organic polymer compound described below, and then emulsified or dispersed in an aqueous medium to prepare an emulsified dispersion of the compound, or these compounds may be separately added to an aqueous medium and mixed therein.

The amount of the compound of formula (IV) is from 0.1 to 100 wt.%, preferably from 1 to 50 wt.%, and more preferably from 2 to 20 wt.% of the cyan coupler of formula (I). Furthermore, the compounds represented by formula (IV) can be used independently or in combinations thereof.

The high boiling organic solvent having a viscosity of not less than 200 cp (at 25°C) is preferably selected from compounds of the following formulas (IIs) (IIIs), (IVs), (Vs), (VIs) or (VIIs)

wherein W₁, W₂ and W₃ each represent a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, aryl or heterocyclic group; W₄ represents -W₁, -O-W₁ or -S-W₁; n represents an integer of 1 to 5, when n represents 2 or more, the two or more W₄ groups may be identical or different from each other; W₁ and W₂ in formula (VIs) may be bonded to form a condensed ring; W₅ represents a substituted or unsubstituted alkyl, cycloalkyl or aryl group and the total number of carbon atoms in W₅ is not less than 12; and X represents a halogen atom.

When the group represented by W₁, W₂, W₃ or W₅ has a substituent, this substituent may be a group containing one or more bonding groups selected from

wherein R₁₁ represents a 2- to 6-valent group obtained by elimination of hydrogen atom(s) from a phenyl group, and -O-.

The alkyl group represented by W₁, W₂, W₃, W₄ or W₅ may be a straight chain or branched alkyl group (e.g., methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl or icosyl).

Suitable examples of substituents for the alkyl group include a halogen atom, a cycloalkyl group, an aryl group and an ester group. More specifically, suitable examples of the substituted alkyl group include an alkyl group substituted with a halogen atom (e.g., F, Cl or Br) (e.g., -C₂HF₄, -C₅H₃F₁₈, -C₄H₃F₁₆, -C₂H₄Cl, -C₃H₃Cl, -C₃H₅Cl₂, -C₃H₅ClBr or -C₃H₅Br₂); an alkyl group substituted with a cycloalkyl group (e.g.,

substituted; an alkyl group which is substituted with an aryl group (e.g.

substituted; an alkyl group which reacts with a substituent to form a dibasic acid ester (e.g.

-CH₂CH₂COOC₁₂H₂₅, -(CH₂)₄COOC₁₀H₂₁, -(CH₂)₄COOCH₂(CF₂CF₂)₂H, -(CH₂)₇COOC₄H₆, -(CH₂)₃COOC₄H₆, or -(CH₂)₈COO- C₁₂H₅); an alkyl group which is substituted with a substituent to form a lactic acid ester

substituted; an alkyl group substituted with a substituent to form a citric acid ester, etc. (e.g.

an alkyl group substituted with a malic acid ester, etc. (e.g. -CH₂CH(OH)COOC₆H₁₃ or -CH₂CH(OH)COOC₆₂H₅₅); an alkyl group substituted with a tartaric acid ester, etc. (e.g. -CH(OH)CH(OH)COOC₈H₁₇, -CH(OH)CH(OH)COOC₆₃H₃₇,

is substituted.

In formula (VIs), W1 and W2 may form an oxirane, oxolane or oxane ring, which may form a condensed ring.

Specific examples of the elements represented by W₁, W₂, W₃, Cycloalkyl group represented by W₄ or W₅

and those for the substituted cycloalkyl group include

Specific examples of the aryl group represented by W₁, W₂, W₃, W₄ or W�5 include

and those for the substituted aryl group include

a.

Specific examples of the alkenyl group represented by W₁, W₂, W₃ or W₄ include -C₄H�7, -C₅H�9, -C₆H₁₁, -C₇H₁₃, -C₄H₁₅, -C₆H₁₅, -C₅₀H₁₅, -C₆H₁₀, -C₅₁₇H₁₃ or C₅₈H₃₅. Suitable examples of substituents of the substituted alkenyl group include a halogen atom (e.g. F, Cl or Br), -OC₈H₁₇, -OC₅₁₇H₁₅,

and specific examples of the alkenyl group include

a.

Specific examples of the heterocyclic group represented by W₁, W₂, W₃ or W₄ include

The boiling point of the high-boiling organic solvent used in the present invention is preferably not less than 140°C, more preferably not less than 160°C.

In the compounds represented by formulas (IIs) to (VIIs), the total number of carbon atoms in W₁ to W₅ is preferably not less than 8.

The term "organic solvent" normally means a liquid compound. However, in the present invention, the organic solvent having a viscosity of not less than 200 cp (at 25ºC) may include a solid compound.

The high boiling point solvent of the present invention is preferably one having a viscosity of not less than 500 cp (at 25°C), more preferably one having a viscosity of not less than 700 cp (at 25°C). Moreover, it is preferably a solid having a melting point of not less than 25°C and is selected from the compounds of formulas (IIs) to (VIIs) as described above. Among them, those of formulas (IIs) and (IIts) are preferred, particularly dialkyl (secondary or tertiary alkyl) or dicycloalkyl esters of phosphoric acid or phthalic acid. Dicycloalkyl esters of phthalic acid are most preferred.

The viscosity of the solvent can be measured using a corn plate type rotational viscometer (VISCONISEMD, manufactured by Tokyo Keiki).

The amount of high-boiling organic solvent to be used may vary greatly depending on the type and amount of cyan coupler used, but it is preferably in the range of 0.05 to 20 parts by weight per part by weight of cyan coupler of the formula (I) according to the invention.

The high boiling point organic solvents of the present invention may be used individually or in combinations with each other or together with other hitherto known high boiling point organic solvents as long as the objects of the present invention are achieved. Suitable examples of such known high boiling point organic solvents include phosphoric acid ester type solvents, e.g. tricresyl phosphate, tri-2-ethylhexyl phosphate, 7-methyloctyl phosphate or tricyclohexyl phosphate, and phenolic solvents, e.g. 2,5-di-tert-amylphenol or 2,5-di-sec-amylphenol.

Specific examples of the high-boiling organic solvents having high viscosity according to the present invention are illustrated below, but the present invention is not limited thereto.

Annotation: C₈H₁₇EH denotes a 2-ethylhexyl group

Of the links of the formula (IIIs), the high-boiling organic solvents represented by the formula (IIIs-1) or (IIIs-2) described below are preferred.

wherein A represents =CH- or =N-; X₁, X₂ and X₃ each represent -H, halogen, -R₁₂, -CH=NOR₁₂, -COR₁₂, -SO₂R₁₂, -Y₁=R₁₂, -Y₁-COR₁₂, -CO-Y₁₋R₁₂, -Y₁₋SO₂R₁₂ or -SO₂-Y₁-R₁₂, or two of X₁, X₂ and X₃ combine with each other to form an atomic group necessary to form a carbon ring or a hetero ring; Y₁ represents -O-, -S- or

R₁₃ represents -H or -R₁₂; R₁₂ represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms (e.g., methyl, ethyl, isopropyl, sec-butyl, tert-butyl, tert-pentyl, 2-ethylhexyl or octadecyl), a substituted or unsubstituted aryl group having 6 to 20 carbon atoms (e.g., phenyl, m-tolyl, p-tolyl, p-hydroxyphenyl or α-naphthyl), or a substituted or unsubstituted heterocyclic group having 2 to 20 carbon atoms (e.g., pyrazolyl, benzoxazolyl, benzothiazolyl, benzotriazole or phenyltetrazolyl); q represents 2, 3 or 4; and p represents 1, 2 or 3, with the proviso that at least one of X₁ and X₂ substituted on the same benzene ring must contain at least 2 non-hydrogen atoms.

Of these compounds represented by the formula (IIIs-1), those in which q is 2 or 4, p is 1, A is =CH-, X₁ is an alkyl group containing 1 to 6 carbon atoms, a heterocyclic group or -COR₁₄ (wherein R₁₄ represents a phenyl group or -OR₁₅; R₁₅ represents an alkyl group having 1 to 6 carbon atoms; X₂ is -H or an alkyl group having 1 to 6 carbon atoms; and X₃ is -H, a methoxy group or an alkyl group having 2 to 6 carbon atoms) are more preferred in the present invention.

Furthermore, those in which X₁ and X₂ are sterically bulky groups are particularly preferred.

Specific examples of the compounds of formula (IIIs-1) used in the present invention are shown below, but the present invention is not limited thereto.

The compounds represented by formula (IIIs-1) are commercially available or can be prepared by known methods as described, for example, in JP-A-62-134642.

wherein X₄ represents a halogen atom (e.g. fluorine, chlorine, bromine or iodine), an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an alkoxycarbonyl group having 2 to 21 carbon atoms; r represents an integer of 0 to 5; R₁₆, R₁₇ and R₁₈ each represent a straight-chain or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms or a heterocyclic group having 3 to 12 carbon atoms, R₁₆ further represents a hydrogen atom, or R₁₇ and R₁₈ may combine with each other to form a ring; and s represents an integer of 1 to 4, when r=2 or more, the two or more X₄ groups are identical or different from each other, when s=2 or more, the two or more

identical or different from each other,

provided that the sum of r and s is not more than 6.

Regarding the formula (IIIs-2), specific examples of X4 include, in addition to the halogen atom described above, an alkyl group (e.g., methyl, ethyl, isopropyl, tert-butyl, cyclopentyl, cyclohexyl, 2-ethylhexyl, dodecyl, benzyl or trifluoromethyl), an alkoxy group (e.g., methoxy, ethoxy, 2-ethylhexyloxy, benzyloxy, dodecyloxy or methoxyethoxy) and an alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, butoxycarbonyl or hexadecyloxycarbonyl).

In formula (IIIs-2), specific examples of R₁₆, R₁₇ and R₁₇ include a straight-chain or branched alkyl group (e.g., methyl, ethyl, trifluoromethyl, Isopropyl, n-propyl, n-butyl, sec-butyl, isobutyl, isopentyl, sec-pentyl, isohexyl or sec-decyl), a cycloalkyl group (e.g. cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, 4-methylcyclohexyl, 4-methylcyclohexenyl 4-tert-butylcyclohexyl, cycloheptyl, menthyl, bornyl or bicyclo[2,2,1]heptan-2-yl), an aralkyl group (e.g. benzyl, 4-methoxybenzyl, 1-naphthylmethyl or phenethyl), an aryl group (e.g. phenyl, 4-methoxyphenyl, 2,4-dichlorophenyl, p-tolyl or 1-naphthyl) or a heterocyclic group (e.g. furyl, thienyl, pyridyl, N-methylimidazolyl, N-methylpyrrolyl, tetrahydrofurfuryl, N-ethylindolyl or quinolyl).

In formula (IIIs-2) include specific examples of

wherein R₁₇ and R₁₈ combine to form a ring, cyclopentyl, cyclohexyl, menthyl, phenyl, bornyl or bicyclo[2,2,1]heptan-2-yl).

Of the compounds represented by the formula (IIIs-2), compounds preferably used in the present invention are those which satisfy the following conditions (1) or (2):

(1) the sum of α-hydrogen atoms in R₁₆, R₁₇ and R₁₇ does not exceed 7, or

(2) when R₁₆ is a hydrogen atom, either (a) when R₁₇ and R₁₈ combine to form a ring, the number of α-hydrogen atoms in R₁₇ and R₁₈ is not more than 1, or (b) when R₁₇ and R₁₈ do not combine to form a ring the α-position of either R₁₇ and R₁₈ is substituted with two different substituents.

Of the compounds represented by the formula (IIIs-2), those in which r=0 and s=2 are more preferred.

Particularly preferred compounds are represented by the formula (IIIs-3) or (IIIs-4):

wherein R₁₆, R₁₇ and R₁₈ each have the same meaning as defined in formula (IIIs-2).

From the groups

in formula (IIIs-2) are In particular, preference is given to those who fulfil the following conditions (3) or (4):

(3) R₁₆, R₁₇ and R₁₈ each represent an alkyl group (including a cycloalkyl group and an aralkyl group), and R₁₆, R₁₇ and R₁₈ are not all simultaneously methyl groups, or

(4) R₁₆ is a hydrogen atom or an alkyl group, and R₁₇ and R₁₈ combine with each other to form a substituted or unsubstituted cyclohexane or cyclohexene ring.

Specific examples of

in formula (IIIs-2) are given below.

Specific examples of compounds of formula (IIIs-2) are listed below, but the present invention is not limited to these.

Specific examples of other compounds of formula (IIIs-2) are listed below: where R represents: where R represents:

The compounds represented by formula (IIIs-2) can be prepared by the following method.

where M represents a hydrogen atom, Li, Na or K

In the process described above, when M is a hydrogen atom, pyridine, triethylamine, tetramethylguanidine, DBN, DBU, sodium carbonate or potassium carbonate can be used as a base. As the reaction solvent, acetonitrile, dimethylformamide, dimethylacetamide, N,N- dimethylimidazolidinone, sulforane, dimethyl sulfoxide, benzene, toluene, xylene, dioxane or tetrahydrofuran are preferably used.

Specific examples of the manufacturing process are described, for example, in EP-OS 228 064.

The water-insoluble organic polymer compound used in the silver halide color photographic material of the present invention has a relative fluorescence efficiency (K value) of not less than 0.10, more preferably not less than 0.20. The larger the value, the better the effect.

The K value described above represents a relative fluorescence quantum efficiency of a compound A having the structure described below, which is a dye conventionally used as a fluorescent probe in a polymer. The K value is defined by the following equation:

K = φa/φb

where φa and φb represent the fluorescence quantum efficiency of compound A in polymer a and polymer b, respectively. Compound A

The fluorescence quantum efficiency can be measured according to the procedure described in Macromolecules, Vol. 14, page 587 (1981). More precisely, the K value was determined from φa and φb, which were measured at room temperature using a thin polymer layer containing 0.5 mmol of compound A as described above (this layer was prepared by spin coating a polymer solution on a slide frame glass in greater thickness, which had an absorbance of 0.05 to 0.1 at the absorption maximum λmax of compound A). According to the invention, the K value was determined using polymethyl methacrylate (average molecular weight 20,000) as polymer b described above.

The polymers that can be used according to the invention are described by the following examples, but the present invention is not limited to these polymers.

(A) Vinyl polymers:

Monomers that can be used to form vinyl polymers that can be used according to the invention include acrylic acid esters, methacrylic acid esters, vinyl esters, acrylamides, methacrylamides, olefins, styrenes, vinyl ethers and other vinyl monomers.

Specific examples of acrylic acid esters include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, sec-butyl acrylate, tert-butyl acrylate, amyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, tert-octyl acrylate, 2-chloroethyl acrylate, 2-bromoethyl acrylate, 4-chlorobutyl acrylate, cyanoethyl acrylate, 2-acetoxyethyl acrylate, dimethylaminoethyl acrylate, benzyl acrylate, methoxybenzyl acrylate, 2-chlorocyclohexyl acrylate, cyclohexyl acrylate, Furfuryl acrylate, tetrahydrofurfuryl acrylate, phenyl acrylate, 5-hydroxypentyl acrylate, 2,2-dimethyl-3-hydroxypropyl acrylate, 2-methoxyethyl acrylate, 3-methoxybutyl acrylate, 2-ethoxyethyl acrylate, 2-isopropoxyethyl acrylate, 2-butoxyethyl acrylate, 2-(2-methoxyethoxy)ethyl acrylate, 2-(2-butoxyethoxy)ethyl acrylate, w-methoxypolyethylene glycol acrylate [addition molar number] n = 9), 1-bromo-2-methoxyethyl acrylate, 1,1-dichloro-2-ethoxyethyl acrylate, etc.

Specific examples of acrylic acid esters include methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, stearyl methacrylate, sulfopropyl methacrylate, n-ethyl-N-phenylaminoethyl methacrylate, 2-(3-phenylpropyloxy)ethyl methacrylate, dimethylaminophenoxyethyl methacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, phenyl methacrylate, cresyl methacrylate, naphthyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, triethylene glycol monomethacrylate, Dipropylene glycol monomethacrylate, 2-methoxyethyl methacrylate, 3-methoxybutyl methacrylate, 2-acetoxyethyl methacrylate, 2-acetoacetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-isopropoxyethyl methacrylate, 2-butoxyethyl methacrylate, 2-(2- methoxyethoxy)ethyl methacrylate, 2-(2- Ethoxyethoxy)ethyl methacrylate, 2-(2-butoxyethoxy)ethyl methacrylate, ω-methoxypolyethylene glycol methacrylate (number of moles added: n = 6), allyl methacrylate, dimethylaminoethyl methacrylate methyl chloride salt, etc.

Specific examples of vinyl esters include vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl caproate, vinyl chloroacetate, vinyl methoxyacetate, vinyl phenyl acetate, vinyl benzoate, vinyl salicylate, etc.

Specific examples of acrylamides include acrylamide, methacrylamide, ethylacrylamide, propylacrylamide, butylacrylamide, tert-butylacrylamide, cyclohexylacrylamide, benzylacrylamide, hydroxymethylacrylamide, methoxyethylacrylamide, dimethylaminoethylacrylamide, phenylacrylamide, dimethylacrylamide, diethylacrylamide, β-cyanoethylacrylamide, N-(2-acetoacetoxyethyl)acrylamide, diacetoneacrylamide, tert-octylacrylamide, etc.

Specific examples of methacrylamides include methacrylamide, methyl methacrylamide, ethyl methacrylamide, propyl methacrylamide, butyl methacrylamide, tert- butyl methacrylamide, cyclohexyl methacrylamide, benzyl methacrylamide, hydroxymethyl methacrylamide, methoxyethyl methacrylamide, dimethylaminoethyl methacrylamide, phenyl methacrylamide, dimethyl methacrylamide, diethyl methacrylamide, β-cyanoethyl methacrylamide, N-(2-acetoacetoxyethyl) methacrylamide, etc.

Specific examples of olefins include dicyclopentadiene, ethylene, propylene, 1-butene, 1-pentene, vinyl chloride, vinylidene chloride, isoprene, chloroprene, butadiene, 2,3-dimethylbutadiene, etc.

Specific examples of styrenes include styrene, methylstyrene, dimethylstyrene, trimethylstyrene, ethylstyrene, isopropylstyrene, chloromethylstyrene, methoxystyrene, acetoxystyrene, chlorostyrene, dichlorostyrene, bromostyrene, methyl vinylbenzoate, etc.

Specific examples of vinyl ethers include methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxyethyl vinyl ether, dimethylaminoethyl vinyl ether, etc.

Specific examples of other vinyl monomers include butyl crotonate, hexyl crotonate, dimethyl itaconate, dibutyl itaconate, diethyl maleate, dimethyl maleate, dibutyl maleate, diethyl fumarate, dimethyl fumarate, dibutyl fumarate, methyl vinyl ketone, phenyl vinyl ketone, methoxyethyl vinyl ketone, glycidyl acrylate, glycidyl methacrylate, N-vinyl oxazolidone, N-vinyl pyrrolidone, acrylonitrile, methacrylonitrile, methylenemalononitrile, vinylidene, etc.

Two or more kinds of monomers (e.g., the monomers described above) may be used together to prepare the polymer of the present invention, depending on the purpose of use (e.g., to improve the solubility thereof). Further, for the purpose of adjusting the color-forming ability and solubility of the polymers, a monomer having an acid group as described below may be used. specified as a comonomer as long as the copolymer is not water-soluble.

Specific examples of such monomers having an acid group include acrylic acid; methacrylic acid; itaconic acid; maleic acid; a monoalkyl itaconate (e.g. monomethyl itaconate, monoethyl itaconate or monobutyl itaconate); a monoalkyl maleate (e.g. monomethyl maleate, monoethyl maleate or monobutyl maleate); citraconic acid; styrenesulfonic acid; vinylbenzylsulfonic acid; vinylsulfonic acid; an acryloyloxyalkylsulfonic acid (e.g. acryloyloxymethylsulfonic acid, acryloyloxyethylsulfonic acid or acryloyloxypropylsulfonic acid); a methacryloyloxyalkylsulfonic acid (e.g. methacryloyloxymethylsulfonic acid, methacryloyloxyethylsulfonic acid or methacryloyloxypropylsulfonic acid); an acrylamidoalkylsulfonic acid (e.g. 2-acrylamido-2- methylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid or 2-acrylamido-2-methylbutanesulfonic acid) a methacrylamidoalkylsulfonic acid (e.g. 2-methacrylamido-2-methylethanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid or 2-methacrylamido-2-methylbutanesulfonic acid); etc.

The acid can be in the form of a salt of an alkali metal (e.g. sodium, potassium) or an ammonium ion.

In the case where the above-described vinyl monomer and a hydrophilic vinyl monomer forming a hydrophilic homopolymer are used as comonomers, the amount of hydrophilic vinyl monomer contained in the copolymer is Monomer is not strictly limited as long as the copolymer is not water-soluble. The amount of hydrophilic monomer is preferably not more than 40 mol%, more preferably not more than 20 mol%, and still more preferably not more than 10 mol%. Further, when a hydrophilic comonomer copolymerizable with the monomer of the present invention has an acid group, the amount of comonomer having an acid group contained in the copolymer is generally not more than 20 mol%, and preferably not more than 10 mol%, from the viewpoint of the image preservability described above. In the most preferred case, the copolymer does not contain such a monomer.

Preferred monomers include methacrylate type monomers, acrylamide type monomers and methacrylamide type monomers. Especially preferred monomers are acrylamide type monomers and methacrylamide type monomers.

(B) Polymers obtained by condensation polymerization or polyaddition reaction:

As polymers obtained by condensation polymerization, polyesters obtained from polyhydric alcohols and polybasic acids and polyamides obtained from diamines and dibasic acids or ω-amino-ω-carboxylic acids are known. As polymers obtained by polyaddition, polyurethanes obtained from diisocyanates and dihydric alcohols are known.

Suitable polyhydric alcohols include a glycol having a structure of HO-R₂₁-OH (wherein R₂₁ represents a hydrocarbon chain having 2 to about 12 carbon atoms, particularly an aliphatic hydrocarbon chain) and a polyalkylene glycol, while suitable polybasic acids include those represented by the formula HOOC-R₂₂-COOH (wherein R₂₂ represents a single bond or a hydrocarbon chain having 1 to about 12 carbon atoms).

Specific examples of the polyhydric alcohols include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, trimethylolpropane, 1,4-butanediol, isobutylenediol, 1,5-pentanediol, neopentyl glycol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,13-tridecanediol, glycerin, diglycerin, triglycerin, 1-methylglycerin, erythritol, mannitol and sorbitol.

Specific examples of polybasic acids include oxalic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonanedicarboxylic acid, decanedicarboxylic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, phthalic acid, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, mesaconic acid, isopimelic acid, cyclopentadiene- maleic anhydride adduct and rosin acid-maleic anhydride adduct.

Specific examples of diamines include hydrazine, methylenediamine, ethylenediamine, trimethylenediamine, tetramethylenediamine, hexamethylenediamine, dodecylmethylenediamine, 1,4-diaminocyclohexane, 1,4- diaminomethylcyclohexane, o-aminoaniline, p-aminoaniline, 1,4-diaminomethylbenzene and di-(4-aminophenyl) ether.

Specific examples of ω-amino-ω-carboxylic acids include glycine, β-alanine, 3-aminopropionic acid, 4-aminobutyric acid, 5-aminopentanoic acid, 11-aminododecanoic acid, 4-aminobenzoic acid, 4-(2-aminoethyl)benzoic acid and 4-(4-aminophenyl)butyric acid.

Specific examples of diisocyanates include ethylene diisocyanate, hexamethylene diisocyanate, m-phenylene diisocyanate, p-phenylene diisocyanate, p-xylene diisocyanate and 1,5-naphthyl diisocyanate.

(C) Other polymers:

Polyesters or polyamides obtained by ring-opening condensation are shown below. Ring-opening condensation polyester or polyamide with the repeating unit of

wherein X₅ represents -O- or -NH-; t represents an integer of 4 to 7 and the -(CH₂)t- chain may be a branched chain.

Suitable monomers for preparing such polymers include β-propiolactone, ε-caprolactone, dimethylpropiolactone, α-pyrrolidone, α-piperidone, ε-caprolactam and α-methyl-ε-caprolactam.

The polymers represented by the formula (P) can also be used:

wherein A₁ represents a repeating unit having at least one bond selected from an ether bond and a -SO₂ bond in its main chain; B represents a repeating unit having at least one bond selected from a

-binding, a

-bond and a -SO₂-bond and an ester bond in the main chain thereof or a single bond which may be identical or different from that of A₁; R₂₃ represents a hydrogen atom, an alkyl group, an aryl group or an aralkyl group, any of which may be substituted; and u represents an integer of 5 or more.

In addition, two or more of the polymers described above may be used in combination.

Among the polymers used in the invention, vinyl polymers are preferred, acrylic polymers are further preferred, and acrylamide type polymers are particularly preferred.

The molecular weight and the degree of polymerization of the polymer used in the present invention do not have a significant influence on the effect of the present invention. However, certain difficulties may occur when the molecular weight is increased. For example, it takes a longer time to dissolve the polymer in any solvent, and furthermore, its emulsification or dispersion becomes difficult due to high viscosity. In addition, coarse grains are formed, resulting in deterioration of the color forming property and the coating property.

If a large amount of any solvent is used to reduce viscosity in order to eliminate these problems, new problems may arise.

From this point of view, the viscosity of the polymer is preferably not more than 5,000 cps, more preferably not more than 2,000 cps when 30 g of the polymer is dissolved in 100 ml of any solvent. Also, the molecular weight of the polymer usable in the present invention is preferably not more than 150,000, more preferably not more than 100,000.

The term "water insoluble" as used herein in relation to the polymer means that the amount by weight of the polymer soluble in 100 g of distilled water is not more than 3 g, preferably not more than 1 g.

The ratio of polymer to any solvent depends on the type of polymer used and can be varied over a wide range depending on its solubility in the any solvent, its degree of polymerization and the coupler solubility. Typically, the any solvent is used in an amount necessary to provide a sufficiently low viscosity so that a solution containing at least a coupler, a high boiling point coupler solvent and the polymer dissolved in the any solvent can be readily dispersed in water or an aqueous solution of a hydrophilic colloid. Since the viscosity of the solution increases with the degree of polymerization of the polymer, it is difficult to predetermine the ratio of the polymer to any solvent independent of the polymer. Typically, however, a ratio of about 1:1 to about 1:50 (by weight) is preferred. The ratio of the polymer of the present invention to a coupler (the cyan coupler represented by formula (I)) is preferably from 1:20 to 20:1, more preferably from 1:10 to 10:1 (by weight).

Specific examples of the polymers usable in the invention are given below, but The present invention is not limited to these polymers.

The polymer according to the invention can be prepared analogously to the preparation examples described below or by similar processes.

MANUFACTURING EXAMPLE 1 Production of polymethyl methacrylate (P-1):

A mixture of 50 g of methyl methacrylate, 0.5 g of sodium polyacrylate and 200 ml of distilled water was heated at 80°C with stirring in a nitrogen atmosphere in a 500 ml three-necked flask. 500 mg of dimethyl azobisisobutyrate was added as a polymerization initiator, thereby initiating polymerization. After polymerization for 2 hours, the polymerization solution was cooled and the spherical polymer was separated by filtration and washed with water to obtain 48.7 g of P-1.

MANUFACTURING EXAMPLE 2 Preparation of poly(N-tert-butylacrylamide) (P-17):

A mixture of 50 g of t-butylacrylamide and 250 mL of toluene was heated to 80°C with stirring in a nitrogen atmosphere in a 500 mL three-necked flask. 10 mL of a toluene solution containing 500 mg of azobisisobutyronitrile was added as a polymerization initiator, thereby initiating polymerization. After polymerization for 3 hours, the polymerization solution was cooled and poured into 1 L of hexane. The solids subsequently precipitated were separated by filtration, washed with hexane and dried with heating under reduced pressure to obtain 47.9 g of P-17.

The oleophilic fine particle dispersion containing the compounds of the present invention (i.e., the oil-soluble cyan coupler represented by the formula (I), the compound represented by the formula (II) or (III) and the compound represented by the formula (IV), and the high-boiling organic solvent having a viscosity of not less than 200 cp (at 25°C) and/or the water-insoluble organic polymer compound, if desired) can be prepared as follows.

The compounds of the present invention are completely dissolved together with photographic additives in any organic solvent. The solution is dispersed in water, preferably in an aqueous solution of a hydrophilic colloid, and more preferably in an aqueous solution of gelatin, with the aid of a dispersant using ultrasonic stirring or a colloid mill, thereby forming fine particles. Then, the dispersion is mixed with a silver halide emulsion.

Alternatively, water or an aqueous solution of a hydrophilic colloid such as an aqueous solution of gelatin is added to any organic solvent containing a dispersant such as a surfactant and the compounds of the present invention, thereby preparing an oil droplet-in-water type dispersion accompanied by phase inversion.

In addition, the prepared dispersion can be mixed with a photographic emulsion after removing any solvent by a suitable method such as distillation, noodle washing or ultrafiltration.

The term "any organic solvent" as used herein means an organic solvent which is capable of forming an emulsified dispersion and which is ultimately substantially removed from the photographic light-sensitive material during the drying step after coating or by the methods described above, and which is an organic solvent having a low boiling point or a solvent having a certain degree of solubility in water and removability by washing with water.

Specific examples of any organic solvents include: lower alkyl acetate such as ethyl acetate and butyl acetate, ethyl propionate, sec-butyl alcohol, methyl ethyl ketone, methyl isobutyl ketone, β-ethoxyethyl acetate, methyl cellosolve acetate, methyl carbitol acetate, methyl carbitol propionate and cyclohexanone.

Furthermore, if desired, an organic solvent that is completely miscible with water, for example, methyl alcohol, ethyl alcohol or tetrahydrofuran, may also be included.

The color photographic light-sensitive material according to the invention may comprise a support on which at least a blue-sensitive silver halide emulsion layer, at least one green-sensitive silver halide emulsion layer and at least one red-sensitive silver halide emulsion layer. In the case of conventional color printing paper, the light-sensitive layers are usually provided on a support in the order described above, but they may be provided in a different order. Further, an infrared-sensitive silver halide emulsion layer may be used in place of at least one of the above-mentioned emulsion layers. Each of the light-sensitive emulsion layers contains a silver halide emulsion sensitive in a corresponding wavelength region and a so-called color coupler containing a dye in the complementary color to the light to which the silver halide emulsion layer is sensitive, that is, yellow, magenta and blue-green, to blue, green and red. This enables color reproduction to be carried out by a subtractive process. The relationship of the photosensitive layer and the color of the dye formed from the coupler can be varied in a manner other than that described above.

Silver halide emulsions used in the present invention are preferably those composed of silver chlorobromide or silver chloride, each of which contains substantially no silver iodide. The term "containing substantially no silver iodide" as used herein means that the silver iodide content of the emulsion is not more than 1 mol%, preferably not more than 0.2 mol%.

The halogen composition may be the same or different among individual grains in the emulsion. If an emulsion having uniform halogen composition among individual grains is used, it is easier to achieve uniform grain properties. Furthermore, with respect to the distribution of the halogen composition within the silver halide emulsion grains, grains having a so-called uniform structure in which the halogen composition is the same in every part of the grain, grains having a so-called layered structure in which the halogen composition of the grain interior (core) differs from that of the shell (including one or more layers) surrounding the core, and grains having a structure in which portions having different halogen compositions are present in a non-layered form in the interior or on the surface of the grains (the portion having a different composition is attached to an edge, corner or face) can be appropriately selected. In order to achieve high sensitivity, it is advantageous to use any of the latter two types of grains instead of the uniformly structured grains. These are also preferred in terms of pressure resistance. In cases where the silver halide grains do not have a uniform structure, the boundary of the portions having different halogen compositions may be sharp or blurred by the formation of solid solutions due to the compositional difference. Furthermore, grains having an intentional continuous change in structure may be used.

Regarding the halogen composition of the silver chlorobromide emulsion, any silver bromide/silver chloride ratio can be used. The ratio can be varied over a wide range depending on the purpose, but emulsions having a silver chloride content ratio of 2 mol% or more are preferably used.

In photosensitive photographic materials suitable for rapid processing, a so-called high silver chloride content emulsion having a high silver chloride content ratio is preferably used. The silver chloride content ratio in such a high silver chloride content emulsion is preferably 90 mol% or more, more preferably 95 mol% or more.

Of such high silver chloride content emulsions, those having a structure in which a local phase of silver bromide is present in the interior and/or on the surface of the silver halide grains in the layered form or in the non-layered form as described above are preferred. Regarding the halogen composition of the local phase described above, it is preferred that the silver bromide content is at least 10 mol%, and more preferably exceeds 20 mol%. The local phase may be present in the interior of the grain or at the edge, corner or face of the surface of the grain. A preferred example is a grain in which epitaxial growth has been carried out at the corner.

On the other hand, for the purpose of minimizing the sensitivity reduction that occurs when pressure is applied to the photographic light-sensitive material, it is preferable to use uniformly structured grains in which the halogen composition distribution is narrow in a high silver chloride content emulsion having a silver chloride content of 90 mol% or more.

Furthermore, for the purpose of reducing the required replenishment amount of developing solution, a silver chloride emulsion having an increased silver chloride content may be used. In such a case, it is preferable to use a nearly pure silver chloride in which the silver chloride content is from 98 to 100 mol%.

The average grain size of the silver halide grains in the silver halide emulsion used in the present invention (the grain size is defined as the diameter of the circle having the same area as the projected area of the grain and is a numerical average) is preferably from 0.1 to 2 µm.

In addition, it is preferable to use a so-called monodisperse emulsion having a grain size distribution in which the coefficient of variation (obtained by dividing the standard deviation of the grain size distribution by the average grain size) is not more than 20%, preferably not more than 15%. Furthermore, it is preferable to use two or more of the above-described monodisperse emulsions in the same layer as a mixture or in the form of superimposed layers, which serves the purpose of achieving a wide exposure latitude.

The silver halide grains contained in the photographic emulsion may have a regular crystal form such as cubic, tetradecahedral, octahedral, etc., or an irregular crystal form such as spherical, tabular, etc., or may have a composite form of these crystal forms. Also, a mixture of grains having different crystal forms may be used. Of these emulsions, those containing the above-described regular crystal form grains in an amount of not less than 50%, preferably not less than 70%, and more preferably not less than 90% are advantageously used in the present invention.

Furthermore, a silver halide emulsion in which tabular silver halide grains having an average aspect ratio (the diameter corresponding to the circle diameter divided by the thickness) of at least 5, preferably at least 8, account for at least 50% of the total projected area of the silver halide grains can be preferably used in the present invention.

The silver chlorobromide emulsion used in the invention can be prepared in any suitable manner, for example according to the methods described in P. Glafkides, Chimie et Physique Photographique, Paul Montel (1967), GF Duffin, Photographic Emulsion Chemistry, The Focal Press (1966), and VL Zelikman et al, Making and Coating Photographic Emulsion, The Focal Press (1964). That is, any method selected from an acid method, a neutral method and an ammonia method may be used.

Soluble silver salts and soluble halogen salts can be reacted with each other by techniques such as a single jet method, a double jet method and a combination thereof. In addition, a method (so-called reverse mixing method) in which silver halide grains are formed in the presence of an excess of silver ions can be used. As a system of the double jet method, a so-called controlled double jet method in which the pag in the liquid phase in which the silver halide is formed is maintained at a predetermined value can also be used. This method provides a silver halide emulsion in which the crystal form is regular and the grain size is almost uniform.

During the step of forming or physically ripening the silver halide grains of the silver halide emulsion used in the present invention, various kinds of multivalent metal ion impurities may be introduced. Suitable examples of the compounds include cadmium salts, zinc salts, lead salts, copper salts, thallium salts, salts or complex salts of Group VIII elements such as iron, ruthenium, rhodium, palladium, osmium, iridium and platinum. In particular, the above-described Group VIII elements are preferably used. The amount of the added Compound can be varied over a wide range depending on the purpose of use, but it is preferably used in a range of 10⁻⁹⁹ to 10⁻² mol per mol of silver halide.

The silver halide emulsions used according to the invention are usually subjected to chemical sensitization and spectral sensitization.

For chemical sensitization, a sulfur sensitization method, e.g., using an unstable sulfur compound; a noble metal sensitization method, e.g., a gold sensitization method; and a reduction sensitization method may be used singly or in combination. The compounds preferably used in chemical sensitization include those described in JP-A-62-215272, page 18, lower right column to page 22, upper right column.

Spectral sensitization is carried out for the purpose of introducing spectral sensitivity in the desired wavelength range into the emulsion of each layer of the photographic light-sensitive material. Spectral sensitization can be carried out by adding a spectral sensitizing dye, which is a dye capable of absorbing light of a wavelength range corresponding to the desired spectral sensitivity. Suitable examples of the spectral sensitizing dyes used are those as described, for example, in FH Harmer, Heterocyclic compounds - Cyanine dyes band related compounds, John Wiley & Sons (New York, London) (1964). Specific examples of the sensitizing dyes and the spectral sensitization methods preferably used are described in JP-A-62-215272, page 22, right upper column to page 38.

The silver halide emulsions used in the present invention may contain various kinds of compounds or their precursors for preventing the occurrence of fogging or for stabilizing the photographic quality during the preparation, storage and/or photographic processing of the photographic light-sensitive material. Preferably used specific examples of these compounds are described in JP-A-62-215272, pages 39 to 72.

The silver halide emulsion used in the present invention may be a so-called surface latent image type emulsion in which latent images are predominantly formed on the surface of the grains, or a so-called internal latent image type emulsion in which latent images are predominantly formed in the interior of the grains.

In the color photographic light-sensitive material of the present invention, in addition to the cyan coupler used in the present invention, a yellow coupler and a magenta coupler which form yellow and magenta colors, respectively, by coupling with the oxidation product of an aromatic primary amine type color developing agent may be used.

Magenta couplers and yellow couplers preferably used in the present invention include those represented by the formulas (MI), (M-II) or (Y):

In formula (M-I), R₇ and R₄ each represent an aryl group; R₈ represents a hydrogen atom, an aliphatic or aromatic acyl group, or an aliphatic or aromatic sulfonyl group; and Y₃ represents a hydrogen atom or a leaving group.

The aryl group represented by R₇ or R₄ is preferably a phenyl group and may be substituted with one or more substituents selected from a halogen atom, an alkyl group, an alkoxy group, an aryloxy group, an acylamino group, an acyl group, a carbamoyl group, a sulfonamido group, a sulfamoyl group, a sulfonyl group, a sulfamide group, an oxycarbonyl group and a cyano group. When two or more substituents are present, they may be identical or different from each other. R₈ is preferably a hydrogen atom, an aliphatic acyl group or an aliphatic sulfonyl group, and more preferably a halogen atom. Y₃ is preferably a leaving group released from a sulfur atom, an oxygen atom or a nitrogen atom, and more preferably a leaving group of the sulfur atom leaving type, for example as described in U.S. Patent No. 4,351,897 and International Application WO 88/04795.

In the formula (M-II), R₁₀ represents a hydrogen atom or a substituent; Y₄ represents a hydrogen atom or a leaving group, preferably a halogen atom or an arylthio group; Za, Zb and Zc each represent a methine group, a substituted methine group, =N- or -NH-, one of the Za-Zb bond and the Zb-Zc bond is a double bond and the other is a single bond; when the Zb-Zc bond is a carbon-carbon double bond, the Zb-Zc bond may be part of a condensed aromatic ring; R₁₀ or Y₄ may also form a polymer, including a dimer or more; and when Za, Zb or Zc is a substituted methine group, the substituted methine group may form a polymer, including a dimer or more.

Of the pyrazoloazole type couplers represented by the formula (M-II), imidazo[1,2-b]pyrazoles as described in U.S. Patent No. 4,500,630 are preferred, and pyrazolo[1,5-b][1,2,4]triazoles as described in U.S. Patent No. 4,540,654 are particularly preferred in view of the lower yellow side adsorption and the light fastness of the dyes formed therefrom.

Further, pyrazolotriazole couplers having a branched alkyl group directly bonded to the 2-, 3- or 6-position of the pyrazolotriazole ring as described in JP-A-61-65245, pyrazoloazole couplers having a sulfonamido group in its molecule as described in JP-A-61-65246, pyrazoloazole couplers having an alkoxyphenylsulfonamido ballast group as described in JP-A-61-147254, and pyrazolotriazole couplers having an alkoxy group or an aryloxy group at the 6-position as described in EP-A1-226 849 and 294 785 are also preferably used.

In formula (Y), R₁₁ represents a halogen atom, an alkoxy group, a trifluoromethyl group or an aryl group; R₁₂ represents a hydrogen atom, a halogen atom or an alkoxy group; A represents -NHCOR₁₃, -NHSO₂R₁₃, -SO₂NHR₁₃, -COOR₁₃ or

(wherein R₁₃ and R₁₄ each represent an alkyl group, an aryl group or an acyl group); and Y₅ represents a leaving group.

The group represented by R₁₂, R₁₃ or R₁₄ may be substituted with one or more substituents selected from the substituents described for R₁. The group represented by Y₅ The leaving group is preferably a leaving group donated from an oxygen atom or a nitrogen atom, and more preferably a leaving group of the nitrogen atom leaving type.

Specific examples of the couplers represented by the general formula (MI), (M-II) or (Y) are listed below, but the present invention is not limited to these.

The magenta coupler and yellow coupler described above are each incorporated into a silver halide emulsion layer constituting a light-sensitive layer in an amount generally in the range of 0.1 to 1.0 mol each, preferably 0.1 to 0.5 mol per mol of silver halide.

In the present invention, the above-described couplers can be added to light-sensitive silver halide emulsion layers by any of various known methods. Usually, they can be added by an oil droplet-in-water dispersion method known as an oil-protected method. For example, the couplers are first dissolved in a solvent and then emulsified and dispersed in an aqueous gelatin solution containing a surfactant. Alternatively, water or an aqueous gelatin solution can be added to a coupler solution containing a surfactant, followed by phase inversion to obtain an oil droplet-in-water dispersion. Further, alkali-soluble couplers can also be added by the so-called Fischer- Dispersion method. The coupler dispersion may be subjected to distillation, noodle washing, ultrafiltration or the like, whereby the organic solvent having a low boiling point is removed, and then mixed with a photographic emulsion.

It is preferable to use as the dispersion medium for the couplers an organic solvent having a high boiling point which has a dielectric constant of 2 to 20 (at 25°C) and a refractive index of 1.5 to 1.7 (at 25°C) and/or a water-insoluble polymer compound.

As the usable high boiling point organic solvent, any compound having a melting point of 100°C or below and a boiling point of 140°C or higher, which is immiscible with water and is a good solvent for the coupler, can be used in addition to the solvents of formulas (IIs), (IIIs), (IVs), (Vs) (VIs) and (VIIs) described above.

The organic solvents with a high boiling point are described in detail in JP-A-62-215272, page 137, right lower column to page 144, right upper column.

Furthermore, these couplers can be emulsified and dispersed in an aqueous solution of a hydrophilic colloid by incorporating them into a loadable latex polymer (such as those described in US Patent No. 4,203,716) in the presence or absence of the above-described organic solvents with high boiling points.

The color photographic light-sensitive material of the present invention may contain a color fog preventing agent such as a hydroquinone derivative, an aminophenol derivative, a gallic acid derivative and an ascorbic acid derivative.

In the color photographic light-sensitive material of the present invention, various color fading preventive agents can be used. More specifically, representative examples of organic color fading preventive agents for cyan, magenta and/or yellow images are hindered phenols (e.g., hydroquinones, 6-hydroxychromans, 5-hydroxycoumarans, spirochromans, p-alkoxyphenols or bisphenols), gallic acid derivatives, methylenedioxybenzenes, aminophenols, hindered amines or ethers or ester derivatives thereof derived from these compounds by silylation or alkylation of the phenolic hydroxy group therein. Furthermore, metal complexes exemplified by (bisalicylaldoxymate) nickel complex and (bis-N,N-dialkyldithiocarbamate) nickel complexes can be used.

Specific examples of the organic color fading inhibitors are described in the following documents.

Hydroquinones: US Patents 2 360 290, 2 418 613, 2 700 453, 2 701 197, 2 728 659, 2 732 300, 2 735 765, 3 982 944 and 4 430 425, GB Patent 1 363 921, US Patents 2 710 801 and 2 816 028; 6-hydroxychromans, 5-hydroxycoumarans and Spirochromans: US Patents 3,432,300, 3,573,050, 3,574,627, 3,698,909 and 3,764,337, JP-A-52-152225; Spiroindane: US Patent 4,360,589; p-Alkoxyphenols: US Patent No. 2,735,765, GB Patent No. 2,066,975, JP-A-59-10539, JP-B-57-19765, etc.; hindered phenols: US-PS 3,700,455, JP-A-52-72224, US-PS 4,228,235, JP-B-52-6623; Gallic acid derivatives, methylenedioxybenzenes and aminophenols: US Patents 3,457,079 and 4,332,886, JP-B-56-21144; hindered amines: US Patents 3,336,135 and 4,268,593, UK Patents 1,326,889, 1,354,313 and 1,410,846, JP-B-51-1420, JP-A-58-114036, JP-A-59-53846 and JP-A-59-78344.

Furthermore, specific examples of the metal complexes are described in US Patents 4,050,938 and 4,241,155 and in GB-A 2,027,731.

The color fading preventing agent is co-emulsified with the corresponding color coupler in an amount of 5 to 100 wt.% of the color coupler amount and incorporated into the light-sensitive layer, whereby its effect is achieved.

To prevent deterioration of the cyan dye image by heat and especially by light, a UV light absorbing agent can be introduced into a cyan color-forming layer or into both layers adjacent to the cyan color-forming layer.

Suitable examples of the UV light absorbing agents used include aryl group-substituted benzotriazole compounds (such as those described in US Patent No. 3,533,794), 4-thiazolidone compounds (e.g. such as in U.S. Patents 3,314,794 and 3,352,681), benzophenone compounds (e.g., those described in JP-A-46-2784), cinnamic acid ester compounds (e.g., those described in U.S. Patents 3,705,805 and 3,707,395), butadiene compounds (e.g., those described in U.S. Patent 4,045,229), and benzoxazole compounds (e.g., those described in U.S. Patents 3,406,070, 3,677,672, and 4,271,307). In addition, ultraviolet light absorbing couplers (e.g., α-naphthol cyan dye-forming couplers) or ultraviolet light absorbing polymers may be used as ultraviolet light absorbing agents. These ultraviolet light absorbing agents may be mordanted into a specific layer.

Among these UV light absorbing agents, the aryl group-substituted benzotriazole compounds described above are preferred.

In the present invention, it is preferable to use these compounds as described above together with the couplers described above, particularly with pyrazoloazole couplers. More specifically, the sole or combined use of a component (F) capable of chemically bonding with the aromatic amine developing agent remaining after color development to form a chemically inactive and substantially colorless compound and/or a compound (G) capable of chemically bonding with the oxidation product of the aromatic amine developing agent remaining after color development to form a chemically inactive and substantially colorless compound is preferred, thereby preventing the occurrence of stains and other undesirable side effects due to the formation of colored Dyes are prevented by the reaction of the colour developing agent or an oxidation product thereof remaining in the photographic layer with the coupler during preservation of the photographic material after processing.

Among the compounds (F), preferred are those which react with p-anisidine with a second-order reaction rate constant k2 (in trioctyl phosphate at 80°C) of 1.0 to 1 x 10-5 L/mol·sec. The second-order rate constant can be measured by a method as described in JP-A-63-158545.

If the constant k2 is larger than the specified range, the compounds are inherently unstable and may be decomposed by reaction with gelatin or water. On the other hand, if the constant k2 is smaller than the above-described range, the reaction rate of the reaction with the residual aromatic amine developing agent is small, and as a result, the degree of prevention of the side effects caused by the residual aromatic amine developing agent is reduced.

Of the compounds (F), preferred are those represented by the formulas (FI) or (FII):

wherein R₁ and R₂ each represent an aliphatic group, an aromatic group or a heterocyclic group; n represents 0 or 1; A represents a group capable of reacting with an aromatic amine developing agent to form a chemical bond; X represents a group capable of being released by the reaction with an aromatic amine developing agent; B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group or a sulfonyl group; Y represents a group capable of accelerating the addition of an aromatic amine developing agent to the compound of formula (FII); or R₁ and X, or Y and R₂ or B may combine to form a cyclic structure.

Among the reactions for forming a chemical bond with the remaining aromatic amine developing agent, a substitution reaction and an addition reaction are typical reactions.

Specific preferred examples of the compounds represented by the formula (FI) or (FII) are described, for example, in JP-A-63-158545, JP-A-62-283338, EP-A-298 321 and EP-A-277 589.

On the other hand, among the compounds (G) capable of forming a chemical bond with the oxidation product of the aromatic amine developing agent remaining after the color development processing, thereby forming a chemically inactive and substantially colorless compound is formed, preferred are those represented by the formula (GI):

R-Z (GI)

wherein R represents an aliphatic group, an aromatic group or a heterocyclic group; and Z represents a nucleophilic group or a group capable of being decomposed in the photographic material to release a nucleophilic group.

Of the compounds of formula (GI), those in which Z is a group having a Pearson's nucleophilicity nCH3I of at least 5 (R.G. Pearson et al, J. Am. Chem. Soc., vol. 90, page 319 (1968)) or a group derived therefrom are preferred.

Specific preferred examples of the compounds of the formula (GI) are described, for example, in EP-A-255 722, JP-A-62-143048, JP-A-62-229145, JP-A-1-230039, JP-A-1-57259, EP-A-298 321 and EP-A-277 589.

Furthermore, combinations of compound (G) and compound (F) are described in detail in EP-A-277 589.

The photographic light-sensitive material of the present invention may contain water-soluble dyes or dyes which become water-soluble at the time of photographic processing as filter dyes or for preventing irradiation or halation or for various other purposes in the hydrophilic colloid layers. Examples of such Dyes include oxonol dyes, hemioxonol dyes, styryl dyes, merocyanine dyes, cyanine dyes and azo dyes. Of these dyes, oxonol dyes, hemioxonol dyes and merocyanine dyes are particularly suitable.

As binders or protective colloids which can be used for the emulsion layers of the color photographic light-sensitive material of the present invention, gelatin is advantageously used, but other hydrophilic colloids can be used alone or together with gelatin.

As gelatin, lime-treated gelatin or acid-treated gelatin can be used in the present invention. Details of the preparation of gelatin are described in Arther Weiss, The Macromolecular Chemistry of Gelatin, published by Academic Press, 1964.

The support usable in the present invention includes those conventionally used in photographic light-sensitive materials, for example, transparent films such as cellulose nitrate films and polyethylene terephthalate films, or reflective supports. Reflective supports are preferably used for the purposes of the present invention.

The term "reflective support" as used in the invention means a support which has the property of increased reflection, which serves the purpose of the silver halide emulsion layer remain clear. Examples of the reflective support include a support on which is coated a hydrophobic resin containing a light-reflecting substance such as titanium oxide, zinc oxide, calcium carbonate or calcium sulfate dispersed therein, and a support composed of a hydrophobic resin containing a light-reflecting substance dispersed therein. More specifically, they include barium oxide coated paper, polyethylene coated paper, polypropylene type synthetic paper, transparent supports such as a glass plate, a polyester film such as a polyethylene terephthalate film, a cellulose triacetate film or a cellulose nitrate film, a polyamide film, a polycarbonate film, a polystyrene film or a vinyl chloride resin having a reflective layer or containing a reflective substance incorporated therein.

Other examples of the usable reflective support are supports having a metal surface with specular reflectivity or diffuse secondary reflectivity. The metal surface preferably has a spectral reflectance of 0.5 or more in the visible wavelength range. The metal surface is preferably prepared by roughening or introducing diffusion reflectivity using metal powders. Suitable examples of the metals include aluminum, tin, silver, magnesium or an alloy thereof. The metal surface includes a metal plate, a metal foil or a thin metal layer obtained by rolling, vacuum evaporation or plating. Among these, a Metal surface obtained by vacuum evaporation of metal on another substrate is preferably used.

It is preferable to provide a waterproof resin layer, particularly a thermoplastic resin layer, on the metal surface. An antistatic layer is preferably provided on the side opposite to the metal surface of the invention on the support. Details of these supports are described in, for example, JP-A-61-210346, JP-A-63-24247, JP-A-63-24251 and JP-A-63-24255.

The appropriate carrier can be suitably selected depending on the desired use.

White pigments are used as the light-reflecting substance, which are carefully kneaded in the presence of a surfactant, and preferably pigments whose surface has been treated with a dihydric, trihydric or tetrahydric alcohol.

For example, the occupied area ratio in percent per certain unit area of fine white pigment particles can be determined in the following typical manner. More specifically, the observed area is divided into adjacent unit areas of 6 x 6 µm, and the occupied area ratio (Ri) (%) of the fine particle projected onto the unit area is measured. The coefficient of variation of the occupied area ratio (%) can be obtained as the Ratio S/R where S is the standard deviation of Ri, and K is the average value of Ri. The number (n) of unit areas is preferably 6 or more. Consequently, the coefficient of variation (S/R) can be obtained by the following equation:

In the present invention, the coefficient of variation of the occupied area ratio (%) of the fine pigment particles is preferably not more than 0.15, more preferably not more than 0.12. When the value is not more than 0.08, the dispersibility of the particles can be considered to be substantially uniform.

The color photographic light-sensitive material of the present invention is preferably subjected to color development, bleach-fixing and water-washing processing or stabilization processing. Alternatively, bleaching and fixing may be carried out separately in contrast to the one-bath processing described above.

The color developing solution used in the present invention contains a known aromatic primary amine color developing agent. Preferred examples thereof are p-phenylenediamine derivatives. Typical examples of p-phenylenediamine derivatives used are shown below, but the present invention is not limited to these.

D-1 N,N-Diethyl-p-phenylenediamine

D-2 2-Amino-5-diethylaminotoluene

D-3 2-Amino-5-(N-ethyl-N-laurylamino)toluene

D-4 4-[N-Ethyl-N-(β-hydroxyethyl)amino]aniline

D-5 2-methyl-4-[N-ethyl-N-(β-hydroxyethyl)amino]aniline

D-6 4-Amino-3-methyl-N-ethyl-N-[β-(methanesulfonamido)ethyl]aniline

D-7 N-(2-Amino-5-diethylaminophenylethyl)methanesulfonamide

D-8 N,N-Dimethyl-p-phenylenediamine

D-9 4-Amino-3-methyl-N-ethyl-N-methoxyethylaniline

D-10 4-Amino-3-methyl-N-ethyl-N-β-ethoxyethylaniline

D-11 4-Amino-3-methyl-N-ethyl-N-β-butoxyethylaniline

Of these p-phenylenediamine derivatives, 4-amino-3-methyl- N-ethyl-N-[(3-(methanesulfonamido)ethyl]aniline (D-6) is particularly preferred.

These p-phenylenediamine derivatives can be in the form of salts, such as sulfates, hydrochlorides, sulfites or p-toluenesulfonates.

The aromatic primary amine developing agent is used in an amount of from about 0.1 to about 20 g/L of developing solution, and preferably from about 0.5 to about 10 g/L.

In the present invention, it is preferable to use a color developing solution which substantially does not contain benzyl alcohol. The term "color developing solution which substantially does not contain benzyl alcohol" as used herein means that the color developing solution preferably does not contain more than 2 ml, more preferably not more than 0.5 ml, and most preferably not containing benzyl alcohol per litre of solution.

The color developing solution used in the present invention further preferably does not contain a substantial amount of sulfite ion. Although sulfite ion acts as a preservative for the color developing agent, it has a solubility-enhancing effect on silver halides and also reacts with the oxidation product of the color developing agent, thereby lowering the dye-forming efficiency. These effects are considered to be one of the reasons for causing the fluctuations in photographic quality due to continuous processing. The term "the color developing solution does not contain a substantial amount of sulfite ion" as used herein means that the color developing solution preferably has a sulfite ion concentration of not more than 3.0 x 10-3 mol/l of solution. It is further preferred that the color developing solution does not contain any sulfite ion, except that in the present invention, a very small amount of sulfite ion is used as an antioxidant in a processing agent kit containing the concentrated color developing agent for preparing the processing solution.

The color developing solution used in the present invention preferably does not contain any substantial amounts of hydroxylamine. This is because hydroxylamine acts as a preservative for the developing solution as well as having a silver developing effect, and it is believed that the Variation in the concentration of hydroxylamine greatly affects the photographic quality. The expression "the color developing solution does not contain substantial amounts of hydroxylamine" as used herein means that the color developing solution preferably has a hydroxylamine concentration of not more than 5.0 x 10⊃min;³ mol/l of solution. It is most preferred that the color developing solution contains no hydroxylamine at all.

The color developing solution used in the present invention preferably contains an organic preservative in place of the above-described hydroxylamine and sulfite ions. The term "organic preservative" as used herein means any organic compound capable of reducing the degradation rate of the aromatic primary amine color developing agent when added to a processing solution for the color photographic materials. More specifically, it includes organic compounds having an effect of preventing oxidation of the color developing agent by air or the like. Among these, hydroxylamine derivatives (excluding hydroxylamine), hydroxamic acids, hydrazines, phenols, α-hydroxyketones, α-aminoketones, saccharides, monoamines, diamines, polyamines, quaternary ammonium salts, nitroxy radicals, alcohols, oximes, diamide compounds and condensed amine rings are particularly effective organic preservatives. Specific examples are given in JP-A-63-4235, JP-A-63-30845, JP-A-63-21647, JP-A-63-44655, JP-A-63-53551, LTP-A-63-43140, JP-A-63-56654, JP-A-63-58346, JP-A-63-43138, JP-A-63-146041, JP-A-63-44657, JP-A-63-44656, US Patent Nos. 3,651,503 and 2,494,903, JP-A-52-143020 and JP-B-48-30496.

Other preservatives such as various metals as described in JP-A-57-44148 and JP-A-57-53749, salicylic acids as described in JP-A-59-180588, alkanolamines as described in JP-A-54-3532, polyethyleneimines as described in JP-A-56-94349, or aromatic polyhydroxy compounds as described in U.S. Patent No. 3,746,544 may be incorporated into the color developing solution if desired. In particular, the addition of alkanolamines such as triethanolamine, dialkylhydroxylamines such as diethylhydroxylamine, hydrazine derivatives or aromatic polyhydroxy compounds is preferred.

Of the organic preservatives described above, hydroxylamine derivatives and hydrazine derivatives (hydrazines and hydrazides) are particularly preferred and described in detail in, for example, JP-A-1-97953, JP-A-1-186939, JP-A-1-186940 and JP-A-1-187557.

Moreover, it is further preferred that the above-described hydroxylamine derivative or hydrazine derivative is used in combination with an amine from the viewpoint of improving the stability of the color developing solution and the resulting improvement in stability during continuous processing. The above-described amines include cyclic amines as described in JP-A-63-239447, amines, as described in JP-A-63-128340, and amines as described in JP-A-1-186939 and JP-A-1-187557.

According to the present invention, the color developing solution preferably contains chloride ions in a range of from 3.5 x 10⁻² to 1.5 x 10⁻¹ mol/l, particularly from 4 x 10⁻² to 1 x 10⁻¹ mol/l of the solution. If the chloride ion concentration is more than 1.5 x 10⁻¹ mol/l, the development tends to be retarded and is therefore not preferable for achieving the object of the present invention in which the high maximum density is provided by rapid processing. On the other hand, a chloride ion concentration of less than 3.5 x 10⁻² mol/l is not preferable in view of preventing fog formation.

Furthermore, the color developing solution used in the present invention preferably contains bromide ion in an amount of 3.0 x 10-5 to 1.0 x 10-3 mol/l of the solution, more preferably 5.0 x 10-5 to 5 x 10-4 mol/l. If the bromide ion concentration is more than 1 x 10-3 mol/l, development tends to be retarded and the maximum density and sensitivity may decrease. On the other hand, if it is less than 3.0 x 10-5 mol/l, it is difficult to sufficiently prevent fog formation.

The chloride ions and bromide ions may be added directly to the color developing agent or they may be released from the light-sensitive material during development processing.

In the case of direct addition to the color developing solution, suitable examples of compounds that provide chloride ions are sodium chloride, potassium chloride, ammonium chloride, lithium chloride, nickel chloride, magnesium chloride, manganese chloride, calcium chloride and cadmium chloride. Among them, sodium chloride and potassium chloride are preferred. The chloride can also be provided by a fluorescent brightening agent added to the color developing solution.

Suitable examples of compounds that provide bromide ions include sodium bromide, potassium bromide, ammonium bromide, lithium bromide, calcium bromide, magnesium bromide, manganese bromide, nickel bromide, cadmium bromide, cerium bromide and thallium bromide. Among these, potassium bromide and sodium bromide are preferred.

When chloride ions and bromide ions are supplied by the light-sensitive material during development processing, they may come from silver halide emulsions or from other additives in the light-sensitive material.

The color developing solution used in the invention has a pH value that is preferably in the range of 9 to 12, and more preferably 9 to 11.0. The color developing solution may also contain any compounds that are known as usable components for developing solutions.

To maintain the pH in the range described above, various types of buffers can preferably be used. Suitable examples These buffers include carbonates, phosphates, borates, tetraborates, hydroxybenzoates, glycine salts, N,N-dimethylglycine salts, leucine salts, norleucine salts, guanine salts, 3,4-dihydroxyphenylalanine salts, alanine salts, aminobutyrate, 2-amino-2-methyl-1,3-propanediol salts, valine salts, proline salts, trishydroxyaminomethane salts and lysine salts.

In particular, carbonates, phosphates, tetraborates and hydroxybenzoates are preferably used because they have excellent solubility and buffering ability in a high pH range above 9, and they have no adverse effect on the photographic quality (e.g., fogging) when added to the color development and they are inexpensively available.

Specific examples of these buffers include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, trisodium phosphate, tripotassium phosphate, disodium phosphate, dipotassium phosphate, sodium borate, potassium borate, sodium tetraborate (borax), potassium tetraborate, sodium o-hydroxybenzoate (sodium salicylate), potassium o-hydroxybenzoate, sodium 5-sulfo-2-hydroxybenzoate (sodium 5-sulfosalicylate) and potassium 5-sulfo-2-hydroxybenzoate (potassium 5-sulfosalicylate). However, the present invention is not limited to these compounds.

The amount of buffer added to the color developing solution is preferably 0.1 mol or more, and more preferably from 0.1 to 0.4 mol/L.

In addition, various chelating agents can be used in the color developing solution of the present invention for the purpose of preventing calcium or magnesium precipitation or increasing the stability of the color developing solution.

Specific examples of the chelating agents used are given below, but the present invention is not limited to them.

Nitrilotriacetic acid

Diethylenetriaminepentaacetic acid

Ethylenediaminetetraacetic acid

N,N,N-trimethylenephosphonic acid

Ethylenediamine-N,N,N',N'-tetramethylenephosphonic acid

trans-cyclohexanediaminetetraacetic acid

1,2-Diaminopropanetetraacetic acid

Glycol ether diaminetetraacetic acid

Ethylenediamine-o-hydroxyphenylacetic acid

2-Phosphonobutane-1,2,4-tricarboxylic acid

1-Hydroxyethylidene-1,1-diphosphonic acid

N,N'-Bis(2-hydroxybenzyl)ethylenediamine-N,N'-diacetic acid

If desired, two or more types of these chelating agents can be used together.

The chelating agent is added to the color developing solution in an amount sufficient to block the metal ions contained therein. For example, a range of about 0.1 to about 10 g per liter of color developing solution is used.

If desired, the color developing solution may contain suitable development accelerators. Examples of suitable development accelerators include thioether type compounds as described in JP-B-37-16088, JP-B-37-5987, JP-B-38-7826, JP-B-44-12380, JP-B-45-9019 and U.S. Patent No. 3,813,247, and p-phenylenediamine type compounds as described in JP-A-52-49829 and JP-A-50-15554; quaternary ammonium salts as described in JP-A-50-137726, JP-B-44-30074, JP-A-56-156826 and JP-A-52-43429; Amine type compounds as described in US Patents 2,494,903, 3,128,182, 4,230,796, 3,253,919, 2,482,546, 2,596,926 and 3,582,346 and JP-B-41-11431; polyalkylene oxides as described in JP-B-37-16088, JP-B-42-25201, US Patent 3,128,183, JP-B-41-11431, JP-B-42-23883 and US Patent 3,532,501; 1-phenyl-3- pyrazolidones; and imidazoles.

The color developing solution used in the present invention may contain suitable antifogging agents if desired. As the antifogging agents, there may be used metal halides such as sodium chloride, potassium bromide and potassium iodide and organic antifogging agents. Representative examples of organic antifogging agents include nitrogen-containing heterocyclic compounds such as benzotriazole, 6-nitrobenzimidazole, 5-nitroisoindazole, 5-methylbenzotriazole, 5-nitrobenzotriazole, 5-chlorobenzotriazole, 2-thiazolylbenzimidazole, 2-thiazolylmethylbenzimidazole, indazole, hydroxyazaindolizine and adenine.

It is preferred that the color developer solution according to the invention contains fluorescent brightening agents As the fluorescent brightening agent, 4,4'-diamino-2,2'-disulfostilbene type compounds are preferred. The amount of the fluorescent brightening agent added is 0 to 5 g, and preferably 0.1 to 4 g, per liter of the color developing solution.

In addition, the color developing solution of the present invention may contain various surfactants such as alkylsulfonic acids, arylsulfonic acids, aliphatic carboxylic acids and aromatic carboxylic acids if desired.

The processing temperature in the color development step used in the present invention is usually 20 to 50°C, and preferably 30 to 40°C. The processing time is usually 20 seconds to 5 minutes, and preferably 30 seconds to 2 minutes. Furthermore, the replenishment amount of the color developing solution is preferably as small as possible and is usually in the range of 20 to 600 ml, preferably 50 to 300 ml, and more preferably 60 to 200 ml, and most preferably 60 to 150 ml per m² of color photographic light-sensitive material.

The desilvering step used in the present invention can be carried out using any of the general steps including a bleaching step-fixing step, fixing step-bleach-fixing step, bleaching step-bleach-fixing step and bleach-fixing step.

The bleaching agents used in the bleaching solutions or bleach-fixing solutions include any conventional bleaching agents. Organic complex salts of iron (III), e.g., complex salts of aminopolycarboxylic acids (e.g., ethylenediaminetetraacetic acid or diethylenetriaminepentaacetic acid), aminopolyphosphonic acids, phosphonocarboxylic acids and organic phosphonic acids or complex salts of organic acids (e.g., citric acid, tartaric acid or malic acid), persulfates and hydrogen peroxide are preferably used. Of these compounds, organic acid complex salts of iron (III) are particularly preferred from the viewpoint of rapid processing and prevention of environmental pollution.

Specific examples of suitable aminopolycarboxylic acids, aminopolyphosphonic acids and organic phosphonic acids suitable for the formation of organic complex salts of iron (III) are given below.

Ethylenediaminetetraacetic acid

Diethylenetriaminepentaacetic acid

1,3-Diaminopropanetetraacetic acid

Propylenediaminetetraacetic acid

Nitrilotriacetic acid

Cyclohexanediaminetetraacetic acid

Methyliminodiacetic acid

Iminodiacetic acid

Glycol ether diaminetetraacetic acid

These compounds can be in the form of salts, such as sodium, potassium, lithium or ammonium.

Of these compounds, iron(III) complex salts of ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid, cyclohexanediaminetetraacetic acid, 1,3- diaminopropanetetraacetic acid or methyliminodiacetic acid are preferred due to their high bleaching power.

The ferric ion complex salts may be used in the form of a complex salt per se, or they may be formed in situ using a ferric salt (e.g., ferric sulfate, ferric chloride, ferric nitrate, ferric ammonium sulfate, or ferric phosphate) and a chelating agent (e.g., an aminopolycarboxylic acid, an aminopolyphosphonic acid, or a phosphonocarboxylic acid). Furthermore, the chelating agent may be used in an excess amount over that required to form a ferric ion complex salt.

Of the iron(III) ion complex salts, aminopolycarboxylic acid iron(III) complex salts are preferred.

The amount of iron(III) complex salt in the solution is from 0.01 to 1.0 mol/l of the solution, preferably 0.05 to 0.50 mol/l of the solution.

In the bleaching solution, the bleach-fixing solution and/or a prebath thereof, various types of compounds can be used as bleaching accelerators. Specific examples of suitable bleaching accelerators include compounds having a mercapto group or a disulfide bond, for example, as described in US-PS 3,893,858, DE-PS 1,290,812, TP-A-53-95630, Research Disclosure, No. 17129 (July 1978); thiourea type compounds as described, for example, in JP-B-45-8506, JP-A-52-20832, JP-A-53-32735 and US-PS 3,706,561; and halides such as iodide ions or bromide ions. These compounds are preferred because of their high bleaching power.

The bleaching solution or bleach-fixing solution used in the present invention may contain rehalogenating agents such as bromides (e.g. potassium bromide, sodium bromide, ammonium bromide), chlorides (e.g. potassium chloride, sodium chloride or ammonium chloride) or iodides (e.g. ammonium iodide). Further, one or more kinds of inorganic acids, organic acids, alkali metal salts thereof or ammonium salts thereof having pH buffering ability (e.g. boric acid, sodium metaborate, acetic acid, sodium acetate, sodium carbonate, potassium carbonate, phosphorous acid, phosphoric acid, sodium phosphate, citric acid, sodium citrate or tartaric acid), anticorrosive agents (e.g. ammonium nitrate or guanidine) may be added if desired.

As fixing agents that can be used in the bleaching solution or bleach-fixing solution, known fixing agents such as thiosulfates (eg sodium thiosulfate or ammonium thiosulfate), thiocyanates (eg sodium thiocyanate or ammonium thiocyanate), thioether compounds (eg ethylenebisthioglycolic acid, 3,6-dithia-1,8-octanediol) and water-soluble silver halide dissolving agents (eg thioureas) are listed. These are used individually or in A combination of two or more of them is used. In addition, a special bleach-fixing solution containing a combination of fixing agent and a large amount of a halide compound such as potassium iodide as described in JP-A-55-155354 can also be used. Preferably, a thiosulfate, particularly ammonium thiosulfate is used.

The amount of fixing agent to be used in the solution is preferably from 0.3 to 2 mol/L of the solution, and more preferably from 0.5 to 1.0 mol/L.

The pH of the bleach-fixing solution or fixing solution used in the present invention is preferably from 3 to 10, and more preferably from 5 to 9.

Furthermore, various kinds of fluorescent brightening agents, defoaming agents and surfactants, polyvinylpyrrolidone or organic solvents (e.g. methanol) can be added to the bleach-fixing solution.

The bleach-fixing solution or fixing solution used in the present invention may contain, as a preservative, compounds capable of releasing sulfite ions, such as sulfites (e.g. sodium sulfite, potassium sulfite or ammonium sulfite), bisulfites (e.g. ammonium bisulfite, sodium bisulfite or potassium bisulfite) or metabisulfites (e.g. potassium metabisulfite, sodium metabisulfite or ammonium metabisulfite). The amount of such a compound to be added is preferably from about 0.02 to about 0.5 mol, and more preferably 0.04 up to 0.40 mol/l of solution, calculated in terms of sulfite ions.

While sulfites can be added as preservatives, other compounds such as ascorbic acid, a carbonyl bisulfite acid adduct or a carbonyl compound can also be added.

Furthermore, buffers, fluorescent brighteners, chelating agents, defoamers or anti-mold agents can be added if desired.

After desilvering processing such as fixing or bleach-fixing, the silver halide color photographic material of the present invention is generally subjected to a water washing step and/or a stabilizing step.

The amount of water required for the water washing step can be adjusted within a wide range depending on the characteristics of the photographic photosensitive materials (due to the components used therein, e.g. couplers), their use, the temperature of the washing water, the number of water washing tanks (stages), the refreshing system such as countercurrent or with the flow, or other various conditions. The relationship between the number of water washing tanks and the amount of water in a multi-stage countercurrent system can be determined by the method described in Journal of the Society of Motion Picture and Television Engineers, Vol. 64, pages 248 to 253 (May 1955). Usually, the number of stages used in a multi-stage countercurrent system is is used, preferably 2 to 6, in particular 2 to 4.

By using a multi-stage countercurrent system, the amount of water for washing can be significantly reduced. For example, it is possible to use 0.5 to 1 liter or less per m² of the photographic light-sensitive material. However, the increase in the standing time of the water in a tank causes the proliferation of bacteria and some problems such as the adhesion of floating matter to the photographic materials occur. In processing the silver halide color photographic material of the present invention, a method for reducing the amounts of calcium and magnesium can be effectively used to solve these problems, as described in JP-A-62-288838. Further, sterilizers can be used, e.g. isothiazolone compounds and thiabendazoles as described in JP-A-57-8542, chlorine type sterilizers such as sodium chloroisocyanurate as described in JP-A-61-120145, benzotriazoles as described in JP-A-61-267761, copper ions, sterilizers as described in Hiroshi Horiguchi, Bokin-Bobai No Kagaku Sankyo Shuppan (1986) Biseibutsu No Mekkin-, Sakiin-, Bobai-Gijutsu, edited by Eiseigijutsu Kai (1982), or Bokin- Bobaizai Jiten, edited by Nippon Bokin-Bobai Gakkai (1986).

In addition, surfactants can be used as agents for uniform drying, and chelating agents, e.g. EDTA, as water softeners in the washing water.

Following the water washing step described above, or without performing the water washing step, the color photographic material may be treated with a stabilizing solution. Compounds having an image stabilizing effect may be added to the stabilizing solution. These compounds include, for example, aldehyde compounds, e.g., formalin, buffers for adjusting the pH of the layer to a value suitable for stabilizing the dyes formed, or ammonium compounds. In addition, various sterilizers or anti-mold agents as described above may be used in the stabilizing solution, thereby preventing the proliferation of bacteria in the solution and imparting mold resistance to the photographic material after processing. In addition, surfactants, fluorescent whitening agents or hardeners may be added to the stabilizing solution.

The photographic light-sensitive material of the present invention can be directly subjected to stabilization processing without undergoing the water washing step. In this case, any method can be used, such as that described in JP-A-57-8543, JP-A-58-14834 and JP-A-60-220345.

Furthermore, a chelating agent can preferably be used, such as 1-hydroxyethylidene-1,1-diphosphonic acid or ethylenediaminetetramethylenephosphonic acid, a magnesium compound or a bismuth compound.

According to the invention, after the silver removal step, a so-called rinsing solution can also be used as a water washing solution or stabilizing solution.

The pH of the washing water or the stabilizing solution used in the processing of the photographic light-sensitive material of the present invention is usually 4 to 10, and preferably 5 to 8. The temperature thereof can be set within a wide range depending on the characteristics of the photographic light-sensitive material or the use thereof. It is usually selected within a range of 15 to 45°C, preferably 20 to 40°C. The processing time of this step can also be set appropriately, but it is preferable to set the time short so that the processing time is shortened. Therefore, it is preferably 15 seconds to 1 minute 45 seconds, more preferably 30 seconds to 1 minute 30 seconds.

It is preferred that the amount of make-up solution is small in view of reducing the operating costs, reducing the amount of waste and the associated processing sizes.

The specific amount of the replenisher is preferably 0.5 to 50 times, more preferably 3 to 40 times the amount of the processing solution transferred from the previous bath per unit area of the photographic light-sensitive material. Alternatively, it is not more than 1 liter, preferably not more than 500 ml/m² of the photographic light-sensitive material. light-sensitive material. Furthermore, the replenisher solution can be added either continuously or in batches.

The solutions used in the water washing step and/or stabilizing step can be used in the preceding steps. For example, in a multi-stage countercurrent system, the washing water surplus is added to a bleach-fixing bath which is a preceding step, and a concentrated solution is added to the bleach-fixing solution, thereby reducing the amount of waste.

According to the present invention, there is provided a silver halide color photographic material which can be rapidly processed and in which the color restoration failure of the cyan dye image is improved and the destruction of the color balance of the images after processing is prevented.

The present invention will be described in more detail with reference to the following examples, but it should not be construed as being limited thereto.

EXAMPLE 1

On a paper support laminated with polyethylene on both sides, the layers shown below were stacked to produce a multilayered color proof paper, which was designated as Sample 101 The coating solutions were prepared in the following manner.

Preparation of the coating solution for the first layer:

19.1 g of yellow coupler (ExY), 4.4 g of color image stabilizer (Cpd-1) and 0.7 g of color image stabilizer (Cpd-7) were dissolved in a mixture of 27.2 ml of ethyl acetate and 8.2 ml of solvent (Solv-1), and the resulting solution was emulsified and dispersed in 185 ml of a 10% aqueous gelatin solution containing 8 ml of a 10% aqueous sodium dodecylbenzenesulfonate solution. Separately, to a silver chlorobromide emulsion (cubic grains, mixture of two emulsions having an average grain size of 0.88 µm and 0.70 µm in a molar ratio of 3:7 in terms of silver, coefficient of variation of grain size: 0.8 and 0.10, respectively, 0.2 mol% of silver bromide based on the total grains is localized on the surface of the grains, respectively), two blue-sensitive sensitizing dyes as shown below were added in an amount of 2.0 x 10⁻⁴ mol/mol of silver in the case of the emulsion with the larger grain size and in an amount of 2.5 x 10⁻⁴ mol/mol of silver in the case of the emulsion with the larger grain size. mol/mol of silver in the case of the emulsion with smaller grain size, and the emulsion was then subjected to sulfur sensitization. The emulsified dispersion described above was mixed with the silver chlorobromide emulsion while controlling the concentration of the resulting mixture so as to form the composition shown below, thus preparing the coating solution for the first layer.

Coating solutions for the second to seventh layers were prepared in a similar manner as described for the coating solution of the first layer.

1-Oxy-3,5-dichloro-s-triazine sodium salt was used as gelatin hardener in each layer.

The following spectral sensitizing dyes were used in each of the emulsion layers. Blue-sensitive emulsion layer:

(amount of each compound added: 2.0 x 10⁻⁴ mol/mol of silver halide in the larger grain size emulsion and 2.5 x 10⁻⁴ mol/mol of silver halide in the smaller grain size emulsion). GREEN-SENSITIVE EMULSION LAYER:

(amount added: 4.0 x 10⊃min;⊃4; mol/mol of silver halide in the emulsion with larger grain size and 5.6 x 10⊃min;⊃4; mol/mol of silver halide in the emulsion with smaller grain size) and

(amount added: 7.0 x 10⊃min;⊃5; mol/mol of silver halide in the larger grain size emulsion and 1.0 x 10⊃min;⊃5; mol/mol of silver halide in the smaller grain size emulsion). Red-sensitive emulsion layer:

(amount added: 0.9 x 10⊃min;⊃4; mol/mol of silver halide in the emulsion with larger grain size and 1.1 x 10⊃min;⊃4; mol/mol of silver halide in the emulsion with smaller grain size).

To the red-sensitive emulsion layer was added the compound shown below in an amount of 2.6 x 10⊃min;³ mol/mol silver halide.

To the blue-sensitive emulsion layer, the green-sensitive emulsion layer and the red-sensitive emulsion layer, 1-(5-methylureidophenyl)-5-mercaptotetrazole was added in amounts of 8.5 x 10⁻⁵ mol, 7.7 x 10⁻⁴ mol, or 2.5 x 10⁻⁴ mol/mol silver halide were added.

Furthermore, 4-hydroxy-6-methyl-1,3,3a,7-tetraazaindene was added to the blue-sensitive emulsion layer and the green-sensitive emulsion layer in amounts of 1 x 10⁻⁴ and 2 x 10⁻⁴ mol/mol of silver halide, respectively.

In addition, the following dyes were added to the emulsion layers to prevent irradiation.

Layer structure:

The composition of each layer is shown below. The numerical values indicate the coating amount of the components in units of g/m². The coating amount of silver halide emulsion is given in units of silver coating amount.

carrier

Polyethylene laminated paper (the polyethylene coating contains a white pigment (TiO2) and a bluish dye (ultramarine) on the side of the first layer)

First layer: blue-sensitive layer

Silver chlorobromide emulsion as described above 0.30

Gelatin 1.86

Yellow coupler (ExY) 0.82

Color Image Stabilizer (Cpd-1) 0.19

Solvent (Solv-1) 0.35

Color Image Stabilizer (Cpd-7) 0.06

Second layer: color mixing prevention layer

Gelatin 0.99

Color mixing preventive agent (Cpd-5) 0.08

Solvent (Solv-1) 0.16

Solvent (Solv-4) 0.08

Third layer: green-sensitive layer

Silver chlorobromide emulsion (cubic grains, mixture of two emulsions with an average grain size of 0.55 µm and 0.39 µm in a molar ratio of 1:3 in units of silver, coefficient of variation of grain size: 0.10 and 0.08, respectively, 0.8 mol% silver bromide, based on the total grains, is localized on the surface of the grains) 0.12

Gelatin 1.24

Purple coupler (ExM) 0.20

Color Image Stabilizer (Cpd-2) 0.03

Color Image Stabilizer (Cpd-3) 0.15

Color Image Stabilizer (Cpd-4) 0.02

Color Image Stabilizer (Cpd-10) 0.02

Solvent (Solv-2) 0.40

Fourth layer: UV absorber layer

Gelatin 1.58

UV light absorbing agent (UV-1) 0.47

Color mixing preventive agent (Cpd-5) 0.05

Solvent (Solv-5) 0.24

Fifth layer: red-sensitive layer

Silver chlorobromide emulsion (cubic grains, mixture of two emulsions with an average grain size of 0.58 µm and 0.45 µm in a molar ratio of 1:4 in units of silver, coefficient of variation of grain size: 0.09 and 0.11, respectively, 0.6 mol% silver bromide, based on the total grains, is deposited on a part of the surface of the

Grains localized) 0.23

Gelatin 1.34

Blue-green coupler (ExC) 0.32

Color Image Stabilizer (Cpd-6) 0.17

Color Image Stabilizer (Cpd-7) 0.40

Additive (Cpd-8) 0.01

Color Image Stabilizer (Cpd-9) 0.05

Solvent (Solv-6) 0.14

Sixth layer: UV absorber layer

Gelatin 0.53

UV light absorbing agent (UV-1) 0.16

Color mixing preventive agent (Cpd-5) 0.02

Solvent (Solv-5) 0.08

Seventh layer: protective layer

Gelatin 1.33

Acrylic-modified polyvinyl alcohol copolymer (modification level: 17%) 0.17

Liquid paraffin 0.03

The compounds used in the layers described above have the chemical structures given below.

Yellow coupler (ExY)

a mix of

and

in a molar ratio of 1:1

Purple Coupler (EXM)

a mix of

in a molar ratio of 1:1

Blue-green coupler (ExC)

a mix of

in a weight ratio of 2:4:4 Color Image Stabilizer (Cpd-1) Color Image Stabilizer (Cpd-2) Color Image Stabilizer (Cpd-3) Color Image Stabilizer (Cpd-4) Color Image Stabilizer (Cpd-5)

Color Image Stabilizer (Cpd-6)

a mix of

in a weight ratio of 2:4:4 Color image stabilizer (Cpd-7), e.g. compound P-17 (average molecular weight 60,000) Additive (Cpd-8), e.g. compound IV-1 Color image stabilizer (Cpd-9), e.g. compound II-3) Color Image Stabilizer (Cpd-10)

UV light absorbing agent (UV-1)

a mix of

in a weight ratio of 4:2:4 solvent (Solv-1)

Solvent (Solv-2)

a mix of

in a volume ratio of 2:1 solvent (Solv-4) Solvent (Solv-5) Solvent (Solv-6), e.g. compound 5-5

Samples 101 to 124 were prepared in the same manner as described for Sample 102, except that the compounds used in the red-sensitive layer were replaced by those shown in Table 1 below, respectively.

Each sample thus prepared was subjected to wedge exposure through a three-color separation filter for sensitometry using a sensitometer (FWH type, manufactured by Fuji Photo Film Co., Ltd.) equipped with a light source having a color temperature of 3200ºK. The exposure amount was 250 CMS and the exposure time was 0.1 second.

The exposed sample was subjected to continuous processing (running test) with a paper processor following the processing steps as described below until the replenishment amount for color development reached twice the volume of the color development tank capacity.

* The amount of replenisher per m² of photographic light-sensitive material

The washing steps were carried out using a three-tank countercurrent system from laundry (3) towards laundry (1).

The composition of each processing solution used is shown below.

The samples thus obtained were used to carry out evaluations 1 and 2 as given below.

Evaluation 1:

The cyan density of the thus obtained color image of each sample was measured with a Fuji densitometer (Model 8509 Type). Then, the samples were subjected to the oxidation treatment described below. Oxidation treatment:

Oxidation bath:

Potassium ferricyanide 59

Water to 1000 ml

After oxidation treatment, the cyan density of each sample was measured again. The cyan density before oxidation treatment, which provided the maximum density after oxidation treatment, was measured and the extent of color recovery failure was determined by comparing the cyan density before oxidation treatment with the cyan density after oxidation treatment.

Evaluation 2:

Each sample processed in the oxidation treatment was subjected to a color fading test using a light fading tester with a xenon lamp (about 250,000 lux) for 24 hours. The cyan density after the fading test at the point which had a cyan density of 2.00 after the oxidation treatment was measured and the difference between these two cyan densities was determined. The results of the Evaluations 1 and 2 are shown in Table 1 together with the compounds used in the red-sensitive layer. TABLE 1 TABLE 1 CONTINUED *1 1:99 mixture (weight) *2 1:1 mixture (weight) Comparison compound (A): Comparison compound (B): (Compound according to JP-A-63-316857) Comparison compound (C): (Connection according to JP-A-63-3i6857) Comparison compound (D): Comparison compound (E): Comparison compound (F): (Compound according to JP-A-63-316857) High boiling solvent (A): High boiling solvent (B)

From the results shown in Table 1, it can be seen that in the sample not containing the compound of formula (II) and/or (III), Dmax after running processing is low and the degree of color restoration failure is high (comparison of sample 109 with the samples of the present invention). In those samples in which the compounds described in JP-A-63-316857, i.e., comparative compounds (B), (C) and (F) were used, there is a problem that the light fading increases significantly as compared with samples not containing these compounds, although the color restoration failure can be reduced. Furthermore, hydroquinone compounds other than those of the present invention show only a small effect of preventing the color restoration failure and a large light fading. In contrast, when the compound of formula (II) of the present invention is used, the color restoration failure can be reduced. (II) or (III), a sufficient effect of preventing color restoration failure can be achieved, and the light fading does not increase significantly. However, in samples in which the compound of formula (IV) is not simultaneously present (samples 107 and 108), there is a problem that Dmax after continuous processing is insufficient.

As is clear from the above results, those samples using the compound of formula (II) and/or (III) together with the compound of formula (IV) improve the color restoration failure and resist light fading while maintaining a sufficiently high color density. It is also clear that the color restoration failure is further improved and the light fading is further suppressed when the high boiling point solvent and/or the organic polymer compound is added.

EXAMPLE 2

Samples 201 to 206 were prepared in the same manner as described for Sample 123 in Example 1, except that the cyan couplers were each changed to the equimolar amounts shown in Table 2 below.

As a result of carrying out the same evaluations as described in Example 1, it is shown that the invention provides a sufficiently high color density as well as good results in terms of the degree of colour restoration failure is not greater than 0.06 and the degree of light fading is not more than 0.09, regardless of the cyan coupler. TABLE 2

EXAMPLE 3

The color papers prepared in Example 2 were imagewise exposed and subjected to continuous processing (running test) with a paper processor according to the processing steps described below until the amount of color development replenisher reached twice the volume of the color development tank capacity. Then, the same color papers exposed in the same manner as described in Example 1 were processed in the same manner.

* The amount of replenisher per m² of photographic light-sensitive material

The stabilization steps were carried out using a four-tank countercurrent system from stabilization (4) to stabilization (1).

The composition of each processing solution used is shown below.

The samples processed in this way were subjected to the same evaluations as described in Example 1. Similar results were obtained.

Although the invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made therein without departing from the scope of the appended claims.

Claims (36)

1. A multilayer silver halide color photographic material comprising a support having thereon a yellow color-forming silver halide emulsion layer, a magenta color-forming silver halide emulsion layer and a cyan color-forming silver halide emulsion layer, wherein the cyan color-forming silver halide emulsion layer contains at least one oil-soluble eluent coupler capable of coupling with an oxidation product of an aromatic primary amine developing agent to form a substantially diffusion-resistant dye and which is represented by the formula (I), at least one compound selected from the compounds of the formulas (II) and (III), and at least one compound of the formula (IV): wherein Y represents -NHCO- or -CONH; R₁ represents an alkyl group, an aryl group, a heterocyclic group or an amino group; X represents a hydrogen atom, a halogen atom, an alkoxy group or an acylamino group; R₂ represents an alkyl group or an acylamino group or, when bonded to X, a non-metal atom forming a 5- to 7-membered ring; Z represents a hydrogen atom or a group capable of being released by coupling with an oxidation product of a developing agent; R₃ and R₄ each represent a halogen atom; R₄ and R₆ each represent an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an amido group, an acyl group, a sulfonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a sulfamoyl group or a sulfoxide group, provided that each of these groups has 6 or more carbon atoms; and R₇, R₈, R₉ and R₁₀ each represent a hydrogen atom, an aliphatic group, an aromatic group, an aliphatic oxycarbonyl group, an aromatic oxycarbonyl group or a carbamoyl group, or R₇ and R₈ or R₈ and R₁₀ may be combined with each other to form a 5- to 7-membered ring , provided that R₇, R₈, R₈ and R₁₀ do not simultaneously represent hydrogen atoms, and the total number of carbon atoms included therein is 8 to 60. 2. A multilayer silver halide color photographic material according to claim I, wherein the group represented by R₁ has one or more substituents selected from an alkyl group, an aryl group, an alkyl or aryloxy group, a carboxy group, an alkyl or arylcarbonyl group, an alkyl or aryloxycarbonyl group, an acyloxy group, a sulfamoyl group, a carbamoyl group, a Sultonamido group, an acylamino group, an imido group, a sulfonyl group, a hydroxy group, a cyano group, a nitro group and a halogen atom. 3. The multilayer silver halide color photographic material according to claim 1, wherein R₂ and X are combined to form a 5- to 7-membered ring. 4. The multilayer silver halide color photographic material according to claim 1, wherein the group capable of being released is a halogen atom, an alkoxy group, an aryloxy group, an acyloxy group, a sulfonyloxy group, an amido group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, an aliphatic or aromatic thio group, an imido group, an N-heterocyclic group or an aromatic azo group. 5. The multilayer silver halide color photographic material according to claim 1, wherein Y represents -NHCO- and R1 represents an alkyl group or an aryl group. 6. The multilayer silver halide color photographic material according to claim 1, wherein R₂ represents an alkyl group having 1 to 15 carbon atoms. 7. The multilayer silver halide color photographic material according to claim 1, wherein Z represents a hydrogen atom or a halogen atom. 8. The multilayer silver halide color photographic material according to claim 1, wherein X represents a halogen atom. 9. The multilayer silver halide color photographic material according to claim 3, wherein the ring is a heterocyclic ring. 10. The multilayer silver halide color photographic material according to claim 1, wherein R₄ and R₆ each represents an alkyl group, an alkylthio group or an amido group. 11. Multilayer silver halide color photographic material according to claim 1, wherein R₃ and R₄ or R₅ and R₆ are present in the 2- and 5-positions. 12. Multilayer color photographic silver halide material according to claim 1, wherein the at least one compound of formula (II) or (III) is present in an amount of 0.1 to 100 mol% based on the cyan coupler. 13. Multilayer color photographic silver halide material according to claim 1, wherein the at least one compound of formula (II) or (III) and the cyan coupler are present in the same oil droplets. 14. The multilayer silver halide color photographic material according to claim 1, wherein the aliphatic or aromatic group included in the group represented by R 7 , R 8 , R 9 or R 10 in formula (IV) has one or more substituents selected from an alkyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, an alkenyloxy group, an acyl group, an ester group, an amido group, a sulfamido group, an imido group, a ureido group, an aliphatic or aromatic sulfenyl group, an aliphatic or aromatic thio group, a hydroxy group, a cyano group, a carboxy group, a nitro group, a sulfo group and a halogen atom. 15. A multilayer silver halide color photographic material according to claim 1, wherein the compound of formula (IV) and the cyan coupler are present in the same oil droplets. 16. Multilayer silver halide color photographic material according to claim 1, wherein the compound of formula (IV) is present in the range of 0.1 to 100% by weight based on the cyan coupler. 17. A multilayer silver halide color photographic material according to claim 1, wherein the Cyan color-forming silver halide emulsion layer further contains a high boiling organic solvent having a viscosity of not less than 200 cp (at 25ºC). 18. A multilayer silver halide color photographic material according to claim 17, wherein the high boiling organic solvent is a compound of the formula (IIs), (IIIs), (IVs), (Vs), (VIs) or (VIIs): where W₁, W₂; W₃ and W₃ each represent a substituted or unsubstituted alkyl, cycloalkyl, alkenyl, aryl or heterocyclic group; W₄ represents -W₁, -OW₁ or -SW₁; n represents an integer of 1 to 5, when n = 2 or more, the two or more W₄ groups may be identical or different from each other; W₁ and W₂ in formula (VIs) may be bonded to each other to form a condensed ring; W₅ represents a substituted or unsubstituted alkyl, cycloalkyl or aryl group, and the total number of carbon atoms in W₅ is not less than 12; and X represents a halogen atom. 19. A multilayer silver halide color photographic material according to claim 18, wherein the high-boiling organic solvent is a compound of the formula (IIs) or (IIIs). 20. A multilayer silver halide color photographic material according to claim 19, wherein the high boiling organic solvent is a compound of the formula (IIIs-1) or (IIIs-2): wherein A represents =CH- or =N-; X₁, X₂ and X₃ each represent -H, halogen, -R₁₂, -CH=NOR₁₂, -COR₁₂, -SO₂R₁₂, -Y₁=R₁₂, -Y₁=COR₁₂, -CO-Y₁₋R₁₂, -Y₁SO₂R₁₂ or -SO₂-Y₁-R₁₂, or two of X₁, X₂ and X₃ combine with each other to form an atomic group necessary for forming a carbon ring or a hetero ring; Y₁ represents -O-, -S- or R₁₃ represents -H or -R₁₂; R₁₂ represents a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 20 hydrogen atoms, or a substituted or unsubstituted heterocyclic group having 2 to 20 carbon atoms; q represents 2, 3 or 4; and p represents 1, 2 or 3, provided that at least one of X₁ and X₂ substituted on the same benzene ring must contain at least 2 non-hydrogen atoms, wherein X₄ represents a halogen atom, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms or an alkoxycarbonyl group having 2 to 21 carbon atoms; r represents an integer of 0 to 5; R₁₆, R₁₇ and R₁₈ each represent a straight-chain or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, an aralkyl group having 7 to 20 Carbon atoms, an aryl group having 6 to 20 carbon atoms or a heterocyclic group having 3 to 12 carbon atoms, R₁₆ further represents a hydrogen atom, or R₁₇ and R₁₇ may combine with each other to form a ring; and s represents an integer of 1 to 4, when r = 2 or more, the two or more X₄ groups are identical or different from each other, when s = 2 or more, the two or more identical or different from each other, provided that the sum of r and s does not exceed 6. 21. A multilayer silver halide color photographic material according to claim 19, wherein the high boiling organic solvent is a compound of the formula (IIIs-3) or (IIIs-4): wherein R₁₆, R₁₇ and R₁₈ are each as defined in formula (IIIs-2). 22. The multilayer silver halide color photographic material according to claim 1, wherein the cyan color-forming silver halide emulsion layer further contains a water-insoluble organic polymer compound. 23. The multilayer silver halide color photographic material according to claim 22, wherein the water-insoluble organic polymer compound has a relative fluorescence efficiency of not less than 0.10. 24. The multilayer silver halide color photographic material according to claim 22, wherein the water-insoluble organic polymer compound is a vinyl polymer. 25. A multilayer silver halide color photographic material according to claim 24, wherein the vinyl polymer is composed of a monomer, selected from a methacrylic acid ester, an acrylamide and a methacrylamide. 26. The multilayer silver halide color photographic material according to claim 1, wherein the silver halide emulsion comprises silver chlorobromide or silver chloride, each containing substantially no silver iodide. 27. A multilayer silver halide color photographic material according to claim 1, wherein the yellow color-forming silver halide emulsion layer contains at least one magenta coupler and the magenta color-forming silver halide emulsion layer contains at least one yellow coupler. 28. A multilayer silver halide color photographic material according to claim 27, wherein the magenta coupler is a compound of the formula (MI): wherein R₇ and R₉ each represent an aryl group, R₈ represents a hydrogen atom, an aliphatic or aromatic acyl group, or an aliphatic or aromatic sulfonyl group; and Y₃ represents a hydrogen atom or a leaving group. 29. A multilayer silver halide color photographic material according to claim 27, wherein the magenta coupler is a compound of the formula (M-II): wherein R₁₀ represents a hydrogen atom or a substituent; Y₄ represents a hydrogen atom or a leaving group; Za, Zb and Zc each represent a methine group, a substituted methine group, =N- or -NH-, either the Za-Zb bond or the Zb-Zc bond is a double bond and the other is a single bond; when the Zb-Zc bond is a carbon-carbon double bond, the Zb-Zc bond may be part of a fused aromatic ring; R₁₀ or Y₄ may also form a polymer including a dimer or more; and when Za, Zb or Zc is a substituted methine group, the substituted methine group may form a polymer including a dimer or more. 30. A multilayer silver halide color photographic material according to claim 27, wherein the yellow coupler is a compound of the formula (Y): wherein R₁₁ represents a halogen atom, an alkoxy group, a trifluoromethyl group or an aryl group; R₁₂ represents a hydrogen atom, a halogen atom or an alkoxy group; A represents -NHCOR₁₃, -NHSO₂R₁₃, -SO₂NHR₁₃, -COOR₁₃ or wherein R₁₃ and R₁₄ each represent an alkyl group, an aryl group or an acyl group; and Y₅ represents a leaving group. 31. The multilayer silver halide color photographic material according to claim 1, wherein the cyan color-forming silver halide emulsion layer further contains an ultraviolet light absorbing agent. 32. The multilayer silver halide color photographic material according to claim 31, wherein the UV light absorbing agent is an aryl group-substituted benzotriazole compound. 33. A multilayer silver halide color photographic material according to claim 27, wherein the magenta color-forming silver halide emulsion layer further contains a compound selected from compound (F) capable of chemically bonding with the aromatic airtin developing agent remaining after color development to obtain a chemically inactive and substantially colorless compound, and compound (G) capable of chemically bonding with the oxidation product of the aromatic amine developing agent remaining after color development, resulting in a chemically inactive and essentially colorless compound. 34. A multilayer silver halide color photographic material according to claim 33, wherein compound (F) is a compound of the formula (FI) or (FTT): wherein R₁ and R₂ each represent an aliphatic group, an aromatic group or a heterocyclic group; n represents 0 or 1; A represents a group capable of reacting with an aromatic amine developing agent to form a chemical bond; X represents a group capable of being released by the reaction with an aromatic amine developing agent; B represents a hydrogen atom, an aliphatic group, an aromatic group, a heterocyclic group, an acyl group or a sulfonyl group; Y represents a group capable of accelerating the addition of an aromatic amine developing agent to the compound of formula (FII); or R₁ and X, or Y and R₂ or B may combine to form a cyclic structure. 35. Multilayer color photographic silver halide material according to claim 33, wherein compound (G) is a compound of the formula (GI): R-Z (GT) wherein R represents an aliphatic group, an aromatic group or a heterocyclic group; and Z represents a nucleophilic group or a group capable of being decomposed in the photographic material to release a nucleophilic group. 36. The multilayer silver halide color photographic material according to claim 1, wherein the support is a reflective support.